JP6306003B2 - Tetraphenylnaphthalocyanine compound, production method and use thereof - Google Patents

Description

The present invention relates to a novel naphthalocyanine compound having excellent visible light transparency and high durability, and uses thereof.
Specifically, it has strong absorption in the near-infrared region, very little absorption in the visible light region, little coloration, high durability against light and heat, soluble in organic solvents, near-infrared absorption filter, security The present invention relates to a novel naphthalocyanine compound that can be widely used for near-infrared absorbing materials such as inks, heat-ray shielding films, interlayer films for laminated glass, and infrared thermosensitive recording materials, and uses thereof, particularly to heat-ray shielding materials.

In recent years, near-infrared absorbing materials have come to be used in a wide range of fields such as optical recording media, near-infrared photosensitizers, photothermal conversion agents, near-infrared cut filters, near-infrared absorbing inks, and heat ray shielding materials.
The ability to absorb near-infrared light in applications such as near-infrared cut filters used for plasma displays, transparent ink used for security, heat ray shielding materials used in automobiles and building windows, plastic laser welding, etc. In addition, there is a growing demand for the development of a near-infrared absorbing material that has a high visible light transmittance and high transparency, that is, little coloration and high transparency, high durability against light and heat, and that dissolves in organic solvents and resins.
Various organic dyes have been studied as such a near-infrared absorbing material, and some aminium compounds, immonium compounds, phthalocyanine compounds, naphthalocyanine compounds have been put into practical use.
In particular, naphthalocyanine compounds have a high ability to absorb near infrared rays and have relatively good visible light transparency. Therefore, various studies have been made as near-infrared absorbing materials for the above purpose.

In Patent Documents 1 and 2, the center metal is perpendicular to the plane of the naphthalocyanine skeleton.
Disclosed are a near-infrared absorbing ink and a plastic material joining method using a naphthalocyanine compound in which a substituent is coordinated at the (axial position). The naphthalocyanine compound used here is described as absorbing near infrared rays and having little visible light absorption, but has a drawback of low durability.
Patent Document 3 discloses a near-infrared absorbing ink composition containing a near-infrared absorber, an ultraviolet absorber, and a polyester resin. As a naphthalocyanine compound-based near-infrared absorber, eight isopentyls at the α-position are disclosed. Palladium naphthalocyanine having an oxy group is used.
Patent Document 4 discloses a method in which a polyester having a specific polymerization catalyst and an infrared absorber is heated and crystallized in a short time with an infrared heater, and has eight butoxy groups at the α-position as the infrared absorber. Vanadyl naphthalocyanine is used. Since these naphthalocyanine compounds having an alkoxy group at the α-position have little absorption in the visible light region, they are characterized by little coloration and high transparency, but they have the disadvantage of low durability and visible light. Transparency is not sufficient.

Patent Document 5 discloses a heat-absorbing layer system that is used as a heat-blocking thermoplastic plastic that can be used in place of automobile window glass and the like and that contains naphthalocyanine or the like as an infrared absorber. Here, vanadyl-5,14,23,32-tetraphenyl-2,3-naphthalocyanine (vanadyl naphthalocyanine having four phenyl groups at the α-position) is used as a naphthalocyanine-based infrared absorber. The naphthalocyanine compound is excellent in near-infrared absorption ability and transparency (visible light transmission property), but has insufficient light fastness.
Patent Document 6 discloses a naphthalocyanine dye compound having four substituted phenyl groups at the α-position, specifically a vanadyl naphthalocyanine compound having a phenyl group having a nitro group or an acetamide group as a substituent at the α-position. Is disclosed. The naphthalocyanine compound is described as being excellent in light stability while maintaining invisibility, but according to the inventors' additional test, solvent solubility and resin compatibility are poor and processability is poor. There is also a problem that invisibility is insufficient. In Patent Document 6, the compound represented by the general structural formula described in the Markush method includes formally a halogen group as a substituent that the phenyl group may have. There is no specific description of a compound having such a combination of substituents.
Patent Document 7 discloses a tetraazaporphyrin compound obtained by adding one or two molecules of a naphthalene derivative to a naphthalocyanine compound having four substituted phenyl groups at the α-position, and has a characteristic absorption around 750 to 850 nm. However, it is soluble in a solvent and stable to heat and light. However, such a compound has a problem that the added naphthalene derivative is easily oxidized and easily deteriorated, so that the compound is easily discolored.

JP-A-3-079683 JP 2004-231832 A JP 7-216275 A JP 2005-105190 A JP-T-2004-525802 JP 2009-29955 A JP-A-2-134386

  The problem of the present invention is that it has a strong absorption in the near-infrared region, very small absorption in the visible light region, high fastness such as light resistance and heat resistance, and good solubility in organic solvents and resins. Naphthalocyanine compound, and its use such as heat ray shielding material.

〔式（１）中、Ｍは２個の水素原子、２価の金属又は３価もしくは４価の金属の誘導体を表し、Ｒ₁〜Ｒ_４はそれぞれ独立に水素原子、ハロゲン原子又はアルキル基を表し、Ａは式（Ｂ）を表す。〕

〔式（Ｂ）中、Ｘ₁、Ｘ_２はそれぞれ独立に水素原子、フッ素原子又はフッ素原子が置換したアルキル基を表し、Ｘ_１及びＸ_２が同時に水素原子であることは無い。〕As a result of intensive studies on the above problems, the present inventors have found that a tetraphenylnaphthalocyanine compound having a specific structure satisfies the above-described characteristics, and have completed the present invention. That is, the present invention
(I) a tetraphenylnaphthalocyanine compound represented by the general formula (1),

[In the formula (1), M represents two hydrogen atoms, a divalent metal or a trivalent or tetravalent metal derivative, and R _{1 to} R ₄ each independently represents a hydrogen atom, a halogen atom or an alkyl group. A represents formula (B). ]

[In Formula (B), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group substituted with a fluorine atom, and X ₁ and X ₂ are not simultaneously hydrogen atoms. ]

〔式（１）−ａ〜（１）-ｄ中、Ｍ、Ｒ₁〜Ｒ_４、Ａは前記一般式（１）におけるものと同義である。〕(Ii) a tetraphenylnaphthalocyanine compound of (i), which is at least one selected from general formulas (1) -a to (1) -d,

[In the formulas (1) -a to (1) -d, M, R _{1 to} R ₄ and A have the same meanings as those in the general formula (1). ]

〔式（１）−ａ中、Ｍ、Ｒ₁〜Ｒ_４、Ａは前記一般式（１）におけるものと同義である。〕
（iv）Ｘ₁、Ｘ_２が水素原子、フッ素原子又はトリフルオロメチル基である、(ｉ)〜（iii）のいずれかのテトラフェニルナフタロシアニン化合物、
（ｖ）Ｒ_１〜Ｒ_４が水素原子、ハロゲン原子又は炭素数1〜１２のアルキル基である(ｉ)〜(iv)のいずれかのテトラフェニルナフタロシアニン化合物、
（vi）Ｍが２個の水素原子、Ｐｄ、Ｃｕ、Ｚｎ、Ｐｔ、Ｎｉ、ＴｉＯ、Ｃｏ、Ｆｅ、Ｍｎ、Ｓｎ、Ａｌ−Ｃｌ、ＶＯ又はＩｎ−Ｃｌである(ｉ)〜(ｖ)のいずれかのテトラフェニルナフタロシアニン化合物、(Iii) a tetraphenylnaphthalocyanine compound of (i) or (ii) represented by general formula (1) -a,

[In the formula (1) -a, M, R _{1 to} R ₄ and A have the same meanings as those in the general formula (1). ]
(Iv) The tetraphenylnaphthalocyanine compound according to any one of (i) to (iii), wherein X ₁ and X ₂ are a hydrogen atom, a fluorine atom or a trifluoromethyl group,
(V) the tetraphenylnaphthalocyanine compound according to any one of (i) to (iv), wherein R _{1 to} R ₄ are a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms;
(Vi) M is two hydrogen atoms, Pd, Cu, Zn, Pt, Ni, TiO, Co, Fe, Mn, Sn, Al—Cl, VO, or In—Cl. (I) to (v) Any tetraphenylnaphthalocyanine compound,

〔式（２）中、Ｒ₁〜Ｒ_４はそれぞれ独立に水素原子、ハロゲン原子又はアルキル基を表し、Ａは式（Ｂ）を表す。〕

〔式（Ｂ）中、Ｘ₁、Ｘ_２はそれぞれ独立に水素原子、フッ素原子又はフッ素原子が置換したアルキル基を表し、Ｘ_１及びＸ_２が同時に水素原子であることは無い。〕
（xi）一般式(３)で表される１,３−ジイミノベンゾインドリン化合物、

〔式（３）中、Ｒ₁〜Ｒ_４はそれぞれ独立に水素原子、ハロゲン原子又はアルキル基を表し、Ａは式（Ｂ）を表す。〕

〔式（Ｂ）中、Ｘ₁、Ｘ_２はそれぞれ独立に水素原子、フッ素原子又はフッ素原子が置換したアルキル基を表し、Ｘ_１及びＸ_２が同時に水素原子であることは無い。〕
（xii）（ｉ）〜（viii）のいずれかのテトラフェニルナフタロシアニン化合物を含有することを特徴とする近赤外線吸収材料、
（xiii）（ｉ）〜（viii）のいずれかのテトラフェニルナフタロシアニン化合物を含有することを特徴とする熱線遮蔽材、
（xiv）熱線遮蔽フィルムである（xiii）の熱線遮蔽材、
（xv）合わせガラス用中間膜である（xiii）の熱線遮蔽材、
に関する。(Vii) Represented by the general formula (1) -a, X ₁ and X ₂ are a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R _{1 to} R ₄ are a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. And the tetraphenylnaphthalocyanine compound of any one of (i) to (vi), wherein M is Cu,
(Viii) Represented by the general formula (1) -a, X ₁ and X ₂ are trifluoromethyl groups, R ₁ , R ₂ and R ₄ are hydrogen atoms, and R ₃ has ₃ to 8 carbon atoms. A tetraphenylnaphthalocyanine compound of any one of (i) to (vii), which is a branched alkyl group and M is Cu;
(Ix) at least one selected from a naphthalene-2,3-dicarbonitrile compound represented by the general formula (2) and a 1,3-diiminobenzoindoline compound represented by the general formula (3), and a metal Or a method for producing a tetraphenylnaphthalocyanine compound according to any one of (i) to (viii), wherein a metal derivative is reacted;
(X) a naphthalene-2,3-dicarbonitrile compound represented by the general formula (2),

[In Formula (2), R < ₁ > -R < ₄ > represents a hydrogen atom, a halogen atom, or an alkyl group each independently, and A represents Formula (B). ]

[In Formula (B), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group substituted with a fluorine atom, and X ₁ and X ₂ are not simultaneously hydrogen atoms. ]
(Xi) 1,3-diiminobenzoindoline compound represented by the general formula (3),

[In Formula (3), R < ₁ > -R < ₄ > represents a hydrogen atom, a halogen atom, or an alkyl group each independently, and A represents Formula (B). ]

[In Formula (B), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group substituted with a fluorine atom, and X ₁ and X ₂ are not simultaneously hydrogen atoms. ]
(Xii) a near-infrared absorbing material comprising the tetraphenylnaphthalocyanine compound of any one of (i) to (viii),
(Xiii) a heat ray shielding material comprising the tetraphenylnaphthalocyanine compound of any one of (i) to (viii),
(Xiv) a heat ray shielding material of (xiii) which is a heat ray shielding film,
(Xv) a heat ray shielding material of (xiii) which is an interlayer film for laminated glass,
About.

  According to the present invention, a naphthalocyanine compound having strong absorption in the near-infrared region, very small absorption in the visible light region, high durability, and good solubility in organic solvents and resins, and such characteristics It has become possible to provide applications such as near infrared absorbing materials and heat ray shielding materials.

1 is an H-NMR spectrum diagram of the compound (2) -11 produced in Example 1. FIG. 4 is a H-NMR spectrum diagram of the compound (2) -18 produced in Example 2. FIG. 4 is a H-NMR spectrum diagram of the compound (2) -31 produced in Example 4. FIG. 4 is an absorption spectrum diagram of compound (1) -7 produced in Example 9. FIG. 4 is an absorption spectrum diagram of compound (1) -8 produced in Example 10. FIG. 4 is a H-NMR spectrum of the compound (1) -34 produced in Example 11. FIG. 4 is an absorption spectrum diagram of compound (1) -34 produced in Example 11. FIG. 2 is an absorption spectrum diagram of compound (1) -36 produced in Example 12. FIG. 2 is an absorption spectrum diagram of compound (1) -26 produced in Example 13. FIG. 2 is an absorption spectrum diagram of compound (1) -27 produced in Example 14. FIG. 2 is an absorption spectrum diagram of compound (1) -29 produced in Example 15. FIG. 2 is an absorption spectrum diagram of compound (1) -37 produced in Example 16. FIG. 2 is a H-NMR spectrum of the compound (1) -37-a produced in Example 16. FIG. 4 is a H-NMR spectrum diagram of the compound (1) -37-b produced in Example 16. FIG. 2 is a H-NMR spectrum diagram of the compound (1) -37-c produced in Example 16. FIG. 4 is an absorption spectrum diagram of compound (1) -41 produced in Example 17. FIG. 2 is an absorption spectrum diagram of compound (1) -35 produced in Example 18. FIG. 2 is an absorption spectrum diagram of compound (1) -64 produced in Example 19. FIG. 2 is an absorption spectrum diagram of compound (1) -65 produced in Example 20. FIG. 2 is an absorption spectrum diagram of tetraphenyl-Pd-naphthalocyanine produced in Comparative Example 1. FIG. 6 is a comparison diagram of transmission spectra of the tetraphenylnaphthalocyanine compound of the present invention produced in Example 15 and Example 20 and the compound of Comparative Example 2. FIG.

〔式（１）中、Ｍは２個の水素原子、２価の金属又は３価もしくは４価の金属の誘導体を表し、Ｒ₁〜Ｒ_４はそれぞれ独立に水素原子、ハロゲン原子又はアルキル基を表し、Ａは式（Ｂ）を表す。〕

〔式（Ｂ）中、Ｘ₁、Ｘ_２はそれぞれ独立に水素原子、フッ素原子又はフッ素原子が置換したアルキル基を表し、Ｘ_１及びＸ_２が同時に水素原子であることは無い。〕
上記一般式(１)のテトラフェニルナフタロシアニン化合物は、より具体的には、下記一般式(１)−ａ〜(１)−ｄから選ばれる少なくとも 1 種である。即ち、下記一般式(１)−ａ〜(１)−ｄで表される異性体の１種または２種以上のいずれかの混合物の混合物である。

〔式（１）−ａ〜（１）−Ｄ中、Ｍ、Ｒ_１〜Ｒ_４、Ａは前記一般式（１）におけるものと同義である。〕
上記異性体（１）−ａ〜（１）−Ｄの中でも、（１）−ａで表される異性体が、耐光性、耐熱性などの耐久性が特に高いという特徴を有する点で、好ましい。Hereinafter, the present invention will be described in detail.
[Tetraphenylnaphthalocyanine compound]
1st invention of this invention is the tetraphenyl naphthalocyanine compound represented by General formula (1).

[In the formula (1), M represents two hydrogen atoms, a divalent metal or a trivalent or tetravalent metal derivative, and R _{1 to} R ₄ each independently represents a hydrogen atom, a halogen atom or an alkyl group. A represents formula (B). ]

[In Formula (B), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group substituted with a fluorine atom, and X ₁ and X ₂ are not simultaneously hydrogen atoms. ]
More specifically, the tetraphenylnaphthalocyanine compound of the general formula (1) is at least one selected from the following general formulas (1) -a to (1) -d. That is, it is a mixture of one or two or more of isomers represented by the following general formulas (1) -a to (1) -d.

[In the formulas (1) -a to (1) -D, M, R _{1 to} R ₄ and A have the same meanings as those in the general formula (1). ]
Among the isomers (1) -a to (1) -D, the isomer represented by (1) -a is preferable in that it has characteristics such as particularly high durability such as light resistance and heat resistance. .

〔式（Ｂ）中、Ｘ₁、Ｘ_２はそれぞれ独立に水素原子、フッ素原子又はフッ素原子が置換したアルキル基を表し、Ｘ_１及びＸ_２が同時に水素原子であることは無い。〕
式（Ｂ）中、Ｘ₁、Ｘ_２は水素原子、フッ素原子又はフッ素原子が置換した炭素数１〜１２の直鎖、分岐又は環状のアルキル基が好ましく、水素原子、フッ素原子又はフッ素原子が置換した直鎖、分岐又は環状の炭素数１〜８のアルキル基がより好ましい。Ｘ₁、Ｘ_２は最も好ましくは、トリフルオロメチル基である。In general formula (1) and formula (1) -a to (1) -d, M is preferably two hydrogen atoms, Pd, Cu, Zn, Pt, Ni, TiO, Co, Fe, Mn, Sn Al-Cl, VO or In-Cl. More preferably, M is two hydrogen atoms, Pd, Cu, Zn or VO. Most preferred M is Cu.
In General Formula (1) and Formula (1) -a to (1) -d, R _{1 to} R ₄ are preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms.
R _{1 to} R ₄ are more preferably a hydrogen atom, a fluorine atom, or a branched alkyl group having 3 to 8 carbon atoms.
As what R < ₁ > -R < ₄ > is a halogen atom, although a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom are mentioned, a chlorine atom and a fluorine atom are preferable and a fluorine atom is more preferable.
As R ₁ to R ₄ is an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, more preferably a branched alkyl group having 3 to 8 carbon atoms.
Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl group, n-hexyl group, cyclohexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, 4-methylcyclohexyl group, Examples thereof include linear or branched alkyl groups such as n-octyl group, tert-octyl group, 1-methylheptyl group, and 2-ethylhexyl group.
In the general formula (1) and the general formulas (1) -a to (1) -d, A represents the following formula (B).

[In Formula (B), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group substituted with a fluorine atom, and X ₁ and X ₂ are not simultaneously hydrogen atoms. ]
In the formula (B), X ₁ and X ₂ are preferably a hydrogen atom, a fluorine atom or a linear or branched alkyl group having 1 to 12 carbon atoms substituted by a fluorine atom, and a hydrogen atom, a fluorine atom or a fluorine atom is A substituted linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is more preferred. X ₁ and X ₂ are most preferably a trifluoromethyl group.

本発明の一般式（１）で表されるテトラフェニルナフタロシアニン化合物の具体例を下記表１に示すが、これらに限定されるものではない。
なお、前記したように一般式（１）のテトラフェニルナフタロシアニン化合物は、一般式（１）−ａ〜（１）−ｄで表される異性体の１種または２種以上のいずれかの混合物である。異性体の混合物の場合は、各異性体単品の場合に比べ近赤外線領域の吸収がブロードとなる。熱線遮蔽樹脂などその用途によっては、このように吸収がブロードである異性体の混合物が好ましい。
下記表１に示した具体例は、これらの異性体またはこれらの２種以上の混合物も含む。Examples of the case where X ₁ and X ₂ are alkyl groups substituted with fluorine atoms include fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,3 , 3-tetrafluoropropyl group, 2,2,3,3,3-hexafluoropropyl group, hexafluoroisopropyl group, 4,4,4-trifluorobutyl group, 2,2,3,4,4,4 -Hexafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,5,5,5-pentafluoropentyl group, 2,2,3,3,4,4,5, 5,5-octafluoropentyl group, 2- (perfluorobutyl) ethyl group, 3- (perfluorobutyl) ethyl group, 2- (perfluorohexyl) ethyl group, 3- (perfluorohexyl) butyl group, 2- (Perfluorooctyl) ester Group, 3- (perfluorooctyl) propyl group, 2- (perfluorodecyl) ethyl group, dodecafluoroheptyl group, hexadecafluorononyl group, 4-fluorocyclohexyl group, 4,4-difluorocyclohexyl group, 2, Examples thereof include perfluoroalkyl groups such as 3,4,5,6-pentafluorocyclohexyl group and 3,4-difluorocyclopentyl group.
In the tetraphenylnaphthalocyanine compound represented by the general formula (1), a particularly preferable structure of the compound is represented by the general formula (1) -a, X ₁ and X ₂ are trifluoromethyl groups, R ₁ , R ₂ and R ₄ are hydrogen atoms, R ₃ is a branched alkyl group having 3 to 8 carbon atoms, and M is Cu. In particular, a compound having the following structural formula is preferable in that it has a feature of extremely high durability such as light resistance and heat resistance.

Although the specific example of the tetraphenyl naphthalocyanine compound represented by General formula (1) of this invention is shown in following Table 1, it is not limited to these.
As described above, the tetraphenylnaphthalocyanine compound of the general formula (1) is a mixture of one or more of the isomers represented by the general formulas (1) -a to (1) -d. It is. In the case of a mixture of isomers, the absorption in the near infrared region becomes broader than in the case of each isomer alone. Depending on the application, such as heat ray shielding resin, a mixture of isomers having broad absorption as described above is preferable.
The specific examples shown in Table 1 below also include these isomers or a mixture of two or more thereof.

〔式（２）及び（３）中、Ｒ₁〜Ｒ_４、Ａは前記一般式（１）におけるものと同義である。〕
一般式(２)で表されるナフタレン−２，３−ジカルボニトリル化合物および一般式(３)で表される１，３−ジイミノベンゾインドリン化合物については、それぞれ個別に後述する。[Method for producing tetraphenylnaphthalocyanine compound]
The second invention of the present invention is selected from a naphthalene-2,3-dicarbonitrile compound represented by the general formula (2) and a 1,3-diiminobenzoindoline compound represented by the general formula (3). It is a method for producing a tetraphenylnaphthalocyanine compound of general formula (1) and general formulas (1) -a to (1) -d, in which at least one kind is reacted with a metal or a metal derivative.

[In Formula (2) and (3), R < ₁ > -R < ₄ >, A is synonymous with the thing in the said General formula (1). ]
The naphthalene-2,3-dicarbonitrile compound represented by the general formula (2) and the 1,3-diiminobenzoindoline compound represented by the general formula (3) will be individually described later.

Examples of metals or metal derivatives include Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In, Sn, Pt, Pb, and their halides and carboxylates. , Sulfates, nitrates, carbonyl compounds, oxides, complexes and the like.
In particular, metal halides or carboxylates are preferably used. Examples of these include copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, iron chloride, zinc chloride, odor. Examples thereof include zinc iodide, zinc iodide, zinc acetate, vanadium chloride, vanadium oxychloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride, tin chloride and the like.
The amount of metal or metal derivative used is 0. 1 mol of 1 mol of naphthalene-2,3-dicarbonitrile compound of general formula (6) or 1 mol of 1,3-diiminobenzoindoline compound of general formula (7). 1-fold mole to 0.6-fold mole, preferably 0.2-fold mole to 0.5-fold mole.
The reaction temperature is 60 to 300 ° C, preferably 100 to 220 ° C.
The reaction time is 30 minutes to 72 hours, preferably 1 hour to 48 hours.

In the reaction, it is preferable to use a solvent. The solvent used for the reaction is preferably an organic solvent having a boiling point of 60 ° C. or higher, preferably 80 ° C. or higher.
Examples include methanol, ethanol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, n-amyl alcohol, n-hexanol, 1-heptanol, 1-octanol, 1-dodecanol, benzyl alcohol, ethylene glycol, propylene glycol, ethoxy Alcohol solvents such as ethanol, propoxyethanol, butoxyethanol, dimethylethanol, diethylethanol, dichlorobenzene, trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene, quinoline, DMI (1,3-dimethyl-2-imidazolidinone), urea, etc. Of high boiling point solvents.
The amount of the solvent used is 0.5 to 50 times the volume of the naphthalene-2,3-dicarbonitrile compound of the general formula (2) or the 1,3-diiminobenzoindoline compound of the general formula (3), preferably 1 to 15 times the capacity.

The reaction is carried out in the presence or absence of a catalyst, but is preferably in the presence of a catalyst. Examples of the catalyst include inorganic catalysts such as ammonium molybdate, DBU (1,8-diazabicyclo [5.4.0] -7-undecene), DBN (1,5-diazabicyclo [4.3.0] -5-nonene. Basic organic catalysts such as) can be used. The amount used is 0.01 to 10 times mol, preferably 1 to 2 times mol for 1 mol of naphthalene-2,3-dicarbonitrile compound or 1 mol of 1,3-diiminoisondrine compound.
In the case of a tetraphenyl naphthalocyanine compound in which M is two hydrogen atoms, a naphthalene-2,3-dicarbonitrile compound represented by the general formula (2) and a 1 represented by the general formula (3) After reacting at least one selected from 1,3-diiminobenzoindoline compounds with metallic sodium or metallic potassium under the above reaction conditions, the central metal, sodium or potassium, is removed with hydrochloric acid, sulfuric acid or the like. Can be manufactured.
After completion of the reaction, the solvent is distilled off, or the reaction solution is discharged into a poor solvent for the tetraphenylnaphthalocyanine compound to precipitate the target product, and the precipitate is filtered to filter the tetraphenylnaphthalocyanine of the general formula (1). A compound can be obtained.
Usually, a tetraphenyl naphthalocyanine compound is obtained as a mixture of isomers represented by the general formulas (1) -a to (1) -d.
Depending on the purpose, further purification by a known purification method such as recrystallization or column chromatography can yield a higher-purity target product. Moreover, the target single product can also be isolated from such a mixture of isomers represented by the general formulas (1) -a to (1) -d by such a purification method.
The structure of these isomers can be confirmed by a known analysis method such as X-ray crystal structure analysis.

〔式（２）中、Ｒ₁〜Ｒ_４はそれぞれ独立に水素原子、ハロゲン原子又はアルキル基を表し、Ａは式（Ｂ）を表す。〕

〔式（Ｂ）中、Ｘ₁、Ｘ_２はそれぞれ独立に水素原子、フッ素原子又はフッ素原子が置換したアルキル基を表し、Ｘ_１及びＸ_２が同時に水素原子であることは無い。〕
一般式（２）で表されるナフタレン−２，３−ジカルボニトリル化合物は、前記一般式（１）および一般式（１）−ａ〜（１）−ｄのテトラフェニルナフタロシアニン化合物の製造に用いられる中間体である。
一般式（２）において、Ａの置換基であるＸ₁、Ｘ_２及びＲ₁〜Ｒ_４の好ましい範囲及び具体例は、一般式（１）及び一般式（１）−ａ〜（１）−ｄで示したそれらと同様である。
一般式（６）で表されるナフタレン−２，３−ジカルボニトリル化合物の具体例を下記表２に示すが、これらに限定されるものではない。[Naphthalene-2,3-dicarbonitrile compound]
The third invention of the present invention is a naphthalene-2,3-dicarbonitrile compound represented by the general formula (2).

[In Formula (2), R < ₁ > -R < ₄ > represents a hydrogen atom, a halogen atom, or an alkyl group each independently, and A represents Formula (B). ]

[In Formula (B), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group substituted with a fluorine atom, and X ₁ and X ₂ are not simultaneously hydrogen atoms. ]
The naphthalene-2,3-dicarbonitrile compound represented by the general formula (2) is used for the production of the tetraphenylnaphthalocyanine compounds represented by the general formula (1) and the general formulas (1) -a to (1) -d. The intermediate used.
In the general formula (2), preferred ranges and specific examples of X ₁ , X ₂ and R _{1 to} R ₄ which are substituents of A are the general formula (1) and the general formulas (1) -a to (1)- The same as those indicated by d.
Specific examples of the naphthalene-2,3-dicarbonitrile compound represented by the general formula (6) are shown in Table 2 below, but are not limited thereto.

〔一般式（４）〜（７）において、Ａ及びＲ₁〜Ｒ_４は一般式（２）に示したそれらと同義である。〕The naphthalene-2,3-dicarbonitrile compound represented by the general formula (2) can be produced with reference to known methods relating to known compounds.
For example, with reference to Russian Journal of General Chemistry, Vol 75, No. 5, 2005, pp. 795-799, it can be produced from the 2-methylbenzophenone compound of general formula (4) by the following route.

In [Formula (4) ~ (7), A and R ₁ to R ₄ have the same meanings as those shown in the general formula (2). ]

Specifically, a 2-halogenomethylbenzophenone compound of the general formula (5) is converted into a 2-methylbenzophenone compound of the general formula (4) with a radical generator and a halogenating agent in the presence of an organic solvent, preferably under heating. To do. Next, a condensation reaction is carried out to obtain an isobenzofuran compound of the general formula (6), followed by a Diels-Alder reaction with fumaronitrile to produce a 1,4-dihydro-1,4-epoxynaphthalene compound of the general formula (7). To do. By dehydrating the 1,4-dihydro-1,4-epoxynaphthalene compound with sulfuric acid, a naphthalene-2,3-dicarbonitrile compound of the general formula (2) can be obtained.
In this production method, the naphthalene-2,3 of the general formula (2) is converted from the 2-methylbenzophenone compound of the general formula (4) without isolating the compounds of the general formulas (5), (6), (7). -Dicarbonitrile compounds can be produced in a one-pot system, which is preferable from the viewpoint of reaction yield and operational simplicity.
In the halogenation step of the 2-halogenomethylbenzophenone compound of the general formula (5) from the 2-methylbenzophenone compound of the general formula (4), the amount of radical generator used is 0.01 relative to 1 mol of the 2-methylbenzophenone derivative. The molar ratio is from 3 times to 3 times, preferably from 0.05 times to 2 times, more preferably from 0.05 times to 1 time.

Peroxide-based benzoyl peroxide, di-tert-butyl peroxide and tert-butyl hydroperoxide as radical generators, or azo polymerization initiators V-70, V-65, AIBN, V-59, V -501, V-40, V-30, V-501, VA-044, VA-046B, VA-061, V-50, VA-057, VA-086, VF-096, VAm-110, V-601 Etc. can be used.
The amount of the halogenating agent used is 1 to 10 moles, preferably 1 to 5 moles, more preferably 1 to 5 moles per mole of the 2-methylbenzophenone derivative of the general formula (4). 1 to 3 moles.
As the halogenating agent, bromine, chlorine, N-bromosuccinimide, N-chlorosuccinimide and the like can be used.

The reaction solvent is not particularly limited as long as it does not adversely affect the reaction, and aromatic hydrocarbons such as toluene, xylene, mesitylene, pseudocumene, chlorobenzene, dichlorobenzene, hexane, heptane, cyclohexane, carbon tetrachloride, chloroform, etc. Organic acids such as aliphatic hydrocarbons, acetic acid and trifluoroacetic acid, and aprotic solvents such as DMF, DMAC and DMI can be used.
The amount of the solvent used is 1 to 500 times, preferably 1 to 200 times, more preferably 5 to 100 times the volume of the 2-methylbenzophenone derivative of the general formula (4) used in the reaction.
The reaction temperature in the halogenation step is room temperature to 200 ° C, preferably 50 to 150 ° C, more preferably 50 to 100 ° C.
The reaction time of the halogenation step is 10 minutes to 48 hours, preferably 20 minutes to 24 hours, more preferably 30 minutes to 12 hours.

The 2-halogenomethylbenzophenone compound of the general formula (5) can be isolated by filtering the reaction solution to remove insoluble matters such as succinimide, and then concentrating the solvent under reduced pressure using an evaporator. It is preferable that the reaction solution which is unstable and filtered without being isolated is used as it is and transferred to the next reaction step.
Fumaronitrile is added to the obtained 2-halogenomethylbenzophenone compound of the general formula (5), and when the temperature is raised, an isobenzofuran compound of the general formula (6) is produced, and the Diels-Alder reaction with the fumaronitrile results in the general formula (7). 1,4-dihydro-1,4-epoxynaphthalene compound is produced and dehydrated with sulfuric acid to obtain a naphthalene-2,3-dicarbonitrile compound of the general formula (2).
The reaction temperature of the series of reaction steps is room temperature to 250 ° C, preferably 50 to 200 ° C, more preferably 50 to 150 ° C.
The reaction time of the series of reaction steps is 30 minutes to 48 hours, preferably 1 hour to 24 hours, more preferably 1 hour to 12 hours.
The amount of fumaronitrile used is 1 to 5 moles, preferably 1 to 2 moles, more preferably 1 to 1.5 moles per mole of the 2-methylbenzophenone derivative of the general formula (4). Is a mole.
The amount of sulfuric acid used is 0.05-fold to 5-fold mole, preferably 0.1-fold to 3-fold mole, more preferably 0.2-fold to 1-fold mole with respect to 1 mole of 2-methylbenzophenone derivative. is there.
After completion of all the reactions, most of the solvent is distilled off and dried to obtain a naphthalene-2,3-dicarbonitrile compound of the general formula (2). If necessary, a higher-purity product can be obtained by further adding known purification operations such as recrystallization and column chromatography to the product.

〔式（３）中、Ｒ₁〜Ｒ_４はそれぞれ独立に水素原子、ハロゲン原子又はアルキル基を表し、Ａは式（Ｂ）を表す。〕

〔式（Ｂ）中、Ｘ₁、Ｘ_２はそれぞれ独立に水素原子、フッ素原子又はフッ素原子が置換したアルキル基を表し、Ｘ_１及びＸ_２が同時に水素原子であることは無い。〕
一般式（３）で表される１，３−ジイミノベンゾインドリン化合物は、前記一般式（１）および一般式（１）−ａ〜（１）−ｄのテトラフェニルナフタロシアニン化合物の製造に用いられる中間体である。
一般式(３)において、Ａの置換基であるＸ₁、Ｘ_２及びＲ₁〜Ｒ_４の好ましい範囲及び具体例は、一般式（１）及び一般式(１)−ａ〜(１)−ｄで示したそれらと同様である。
一般式(３)で表される１,３−ジイミノベンゾインドリン化合物の具体例を下記表３に示すが、これらに限定されるものではない。[1,3-Diiminobenzoindoline compound]
The fourth invention of the present invention is a 1,3-diiminobenzoindoline compound represented by the general formula (3).

[In Formula (3), R < ₁ > -R < ₄ > represents a hydrogen atom, a halogen atom, or an alkyl group each independently, and A represents Formula (B). ]

[In Formula (B), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group substituted with a fluorine atom, and X ₁ and X ₂ are not simultaneously hydrogen atoms. ]
The 1,3-diiminobenzoindoline compound represented by the general formula (3) is used for the production of the tetraphenylnaphthalocyanine compounds represented by the general formula (1) and the general formulas (1) -a to (1) -d. Intermediate.
In the general formula (3), preferred ranges and specific examples of X ₁ , X ₂ and R _{1 to} R ₄ which are substituents of A are represented by the general formula (1) and the general formulas (1) -a to (1)- The same as those indicated by d.
Specific examples of the 1,3-diiminobenzoindoline compound represented by the general formula (3) are shown in Table 3 below, but are not limited thereto.

The 1,3-diiminobenzoindoline compound represented by the general formula (3) can be produced with reference to known methods relating to known compounds.
For example, it is produced by reacting a naphthalene-2,3-dicarbonitrile compound represented by the general formula (2) with ammonia in the presence of a metal alkoxide.
The amount of ammonia used is 1 to 20 times mol, preferably 3 to 10 times mol, per mol of naphthalene-2,3-dicarbonitrile compound of general formula (2).
Metal alkoxides include sodium or potassium methoxide, ethoxide, n-propoxide, n-butoxide, n-pentoxide, n-hexyloxyside, n-octyloxyside, 2-methoxyethoxide, 2-ethoxyethoxide. 2-butoxy ethoxide and the like are used.
The amount of metal alkoxide used is 0.01 times to 5 times mol, preferably 0.1 times to 2.0 times mol, relative to the naphthalene-2,3-dicarbonitrile compound of general formula (2). is there.

In the reaction, an organic solvent is preferably used in combination, and an alcohol solvent is usually used as the organic solvent. Examples of alcohol solvents include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol. Used.
The usage-amount of an alcohol solvent is 200 mL-15L with respect to 1 mol of naphthalene-2,3-dicarbonitrile compounds of General formula (2), Preferably it is 500 mL-5L.
In the reaction operation, after adding metal sodium or metal potassium to an alcohol solvent as a reaction solvent to prepare an alcohol solution of metal alkoxide, ammonia and a naphthalene-2,3-dicarbonitrile compound of the general formula (2) Alternatively, ammonia, a naphthalene-2,3-dicarbonitrile compound of the general formula (2) and a separately prepared metal alkoxide may be charged into a reaction solvent to react. You may do it. The amount of the metal used for adjusting the metal alkoxyside is 0.01 times to 5.0 times the mole of the naphthalene-2,3-dicarbonitrile compound of the general formula (2), preferably 0.1 -2.0 times mole.
The reaction temperature is from 0 ° C to the reflux temperature of the solvent, preferably from 20 ° C to the reflux temperature of the solvent. The reaction time is preferably 30 minutes to 72 hours.
After the reaction, the solvent is distilled off, extracted with an aromatic solvent such as toluene or a halogenated hydrocarbon solvent such as methylene chloride, the extract is washed with water, concentrated, and the precipitate is filtered. The 1,3-diiminobenzoindoline compound of (3) can be obtained.

[Near-infrared absorbing material]
Below, the near-infrared absorption material of this invention is demonstrated.
The tetraphenylnaphthalocyanine compound of the present invention is a heat ray shielding material for shielding heat rays, an optical filter for plasma display or liquid crystal display, a flash fixing toner, a photothermal exchange agent for thermal transfer / thermal stencil, etc. Photothermal conversion agents, preheating aids during molding of PET bottles, optical recording media using semiconductor lasers, near infrared absorbing dyes used in optical character readers, photosensitive dyes for tumor treatment, near infrared absorbing filters, etc. It is very useful as a near-infrared absorbing material used in a wide range of applications.
The near-infrared absorbing material of the present invention may be the tetraphenylnaphthalocyanine compound itself of the present invention represented by the general formula (1), or the general formula (1) together with other components such as a binder resin and additives. The tetraphenyl naphthalocyanine compound may be used.
The modes and components of the near infrared absorbing material vary depending on the application and are various.

[Heat ray shielding material]
Below, the heat ray shielding material of this invention is demonstrated.
The tetraphenylnaphthalocyanine compound of the present invention is suitably used for heat ray shielding materials used for films and interlayers used in buildings, automobile windows, etc., greenhouses, sun visors, welding goggles and the like.
The heat ray shielding material of the present invention contains the tetraphenylnaphthalocyanine compound of the present invention represented by the general formula (1).
The tetraphenylnaphthalocyanine compound of the general formula (1) contained in the heat ray shielding material of the present invention may be used as a single compound or in the form of a mixture of two or more. Regarding the isomers, any one of the isomers represented by the general formulas (1) -a to (1) -d may be used, or a mixture of two or more isomers. It may be.
In particular, from the viewpoint of storage stability such as light resistance and heat resistance of the heat ray shielding material, among the isomers represented by the general formulas (1) -a to (1) -d, it is represented by the general formula (1) -a. Those having a high content of isomers are preferred.
For the same reason, X ₁ and X ₂ are preferably a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R _{1 to} R ₄ are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
Furthermore, the thing whose M is Cu is preferable.
Most preferred is a compound represented by the following formula.

The usage form of the heat ray shielding material of the present invention is not particularly limited, and may be any known form. Specific examples include the following examples.
1. 1. Form using molded body itself containing tetraphenylnaphthalocyanine compound of general formula (1) and resin as essential components A mode in which a coating film or a film containing a tetraphenylnaphthalocyanine compound of general formula (1) and a resin as essential components is applied on a base material 3. Between two or more base materials, the general formula (1) 3. Form of laminated body in which a film containing tetraphenylnaphthalocyanine compound and resin as essential components is provided as an intermediate layer. Although it does not restrict | limit especially as a form base material which contained the tetraphenyl naphthalocyanine compound of General formula (1) in a base material, A glass plate; Polycarbonate, Polymethylmethacrylate, Polystyrene, Polyethylene terephthalate, Polyvinyl chloride, Polyethylene Examples thereof include plastic plates such as plate materials such as sulfone and unsaturated polyester.
Among the above forms, in particular 2. A mode in which a coating film or a film containing a tetraphenylnaphthalocyanine compound of the general formula (1) and a resin as essential components is applied on a base material, and between two or more base materials, The form of the laminated body which provided the film etc. which contain the tetraphenyl naphthalocyanine compound of 1) and resin as an essential component as an intermediate | middle layer is preferable.

Thus, the aspect which contains the tetraphenyl naphthalocyanine compound and resin of General formula (1) as an essential component is preferable for the heat ray shielding material of this invention.
The resin can be appropriately selected depending on the intended use of the heat ray shielding material, but is preferably a resin that is substantially transparent and does not significantly absorb and scatter.
Specifically, polycarbonate resin; (meth) acrylic resin such as methyl methacrylate; polyvinyl resin such as polystyrene, polyvinyl chloride, and polyvinylidene chloride; polyolefin resin such as polyethylene and polypropylene; polybutyral resin; acetic acid such as polyvinyl acetate Examples thereof include vinyl resins; polyester resins; polyamide resins; polyvinyl acetal resins; polyvinyl alcohol resins; ethylene-vinyl acetate copolymer resins; ethylene-acrylic copolymer resins; Moreover, as long as it is substantially transparent, not only the above-mentioned one kind of resin but also a blend of two or more kinds of resins can be used, and the above resin can be sandwiched between transparent glasses. .
Among these resins, polycarbonate resin, (meth) acrylic resin, polyester resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, polyvinyl acetal resin, and polyvinyl alcohol resin are preferable, and polycarbonate resin, methacrylic resin, polyethylene terephthalate (PET) are particularly preferable. ) Resin, polyvinyl chloride resin, and polyvinyl acetal resin are more preferable.

  The polycarbonate resin is produced by reacting a dihydric phenol and a carbonate precursor by a solution method or a melting method. The following are mentioned as a typical example of dihydric phenol. 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4 -Hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis ( 4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and the like. Preferred divalent phenols are bis (4-hydroxyphenyl) alkanes, particularly those containing bisphenol as a main component.

Examples of the (meth) acrylic resin include methyl methacrylate alone or a polymerizable unsaturated monomer mixture containing 50% or more of methyl methacrylate or a copolymer thereof. Examples of the polymerizable unsaturated monomer copolymerizable with methyl methacrylate include the following. Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, 2-Methylhydroxy (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, tribromophenyl (meth) acrylate, tetrahydroxyfurfuryl (meth) acrylate, ethylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolethane di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate.

Typical examples of the polyester resin include homopolyesters such as poly C2-4 alkylene terephthalate and poly C2-4 alkylene naphthalate, C2-4 alkylene arylate units (C2-4 alkylene terephthalate and / or C2-4 alkylene naphthalate units). ) As a main component, polyarylate resins, aliphatic polyesters using aliphatic dicarboxylic acids such as adipic acid, and lactone homo- or copolymers such as ε-caprolactone are also included. As an example of the polyester resin, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and the like are preferable in terms of high transparency. Amorphous copolyesters such as C2-4 alkylene arylate copolyesters are also preferred because of their excellent processability. In particular, PET is preferable because it is produced in large quantities and is excellent in heat resistance and strength.
The polyamide resin is a resin having a dehydration polycondensate structure of a diamine compound containing an aromatic or aliphatic group and a dicarboxylic acid compound containing an aromatic or aliphatic group. Here, the aliphatic group also includes an alicyclic aliphatic group. Examples of diamine compounds include hexamethylenediamine, m-xylylenediamine, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, trimethylhexamethylenediamine, bis (aminomethyl) norbornane, Examples thereof include bis (aminomethyl) tetrahydrodicyclopentadiene. Examples of the dicarboxylic acid compounds include adipic acid, dodecanedicarboxylic acid, isophthalic acid, terephthalic acid, bis (hydroxycarbonylmethyl) norbornane, bis (hydroxycarbonylmethyl) tetrahydrodicyclopentadiene, and the like. As the polyamide resin, an amorphous polyamide resin is particularly preferable from the viewpoint of transparency, and resins generally referred to as transparent nylon are preferable.

As the polyvinyl chloride resin, not only a polymer of vinyl chloride monomer but also a copolymer mainly composed of vinyl chloride can be used. Examples of monomers that can be copolymerized with vinyl chloride include vinylidene chloride, ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid, itaconic acid, acrylic acid, and methacrylic acid.
As polyvinyl acetal resin, polyvinyl formal resin obtained by reacting polyvinyl alcohol (PVA) and formaldehyde, polyvinyl acetal resin in a narrow sense obtained by reacting PVA and acetaldehyde, PVA and n-butyraldehyde are reacted. Polyvinyl butyral resin (PVB) obtained by the above, and PVB is preferable. The PVA used for the synthesis of the polyvinyl acetal resin preferably has an average degree of polymerization of 200 to 5000, more preferably 500 to 3000. Moreover, what is 40-85 mol% of acetalization degree is preferable, More preferably, it is a thing of 50-75 mol%.
The polyvinyl alcohol resin can be obtained, for example, by saponifying polyvinyl acetate. The degree of saponification of the polyvinyl alcohol resin is generally in the range of 70 to 99.9 mol%, preferably in the range of 75 to 99.8 mol%, and in the range of 80 to 99.8 mol%. It is more preferable. The average degree of polymerization of the polyvinyl alcohol resin is preferably 500 or more, more preferably 1000 or more and 5000 or less.

The content of the tetraphenylnaphthalocyanine compound of the present invention represented by the general formula (1) in the heat ray shielding material of the present invention varies depending on the thickness of the heat ray shielding material. For example, when producing a heat ray shielding plate having a thickness of 3 mm, 0.002 to 0.06 parts by weight is preferable, more preferably 0.003 to 100 parts by weight of resin blended in the heat ray shielding material. 0.02 part by weight. For example, when producing a heat ray shielding plate having a thickness of 10 mm, 0.0005 to 0.02 parts by weight is preferable with respect to 100 parts by weight of resin, and more preferably 0.001 to 0.005 parts by weight. It is. When producing a 10-micrometer-thick heat ray shielding film, 0.1-20 weight part is preferable with respect to 100 weight part of resin, More preferably, it is 0.5-10 weight part. If the content of the tetraphenylnaphthalocyanine compound of the general formula (1) is displayed regardless of the thickness of the heat ray shielding material, it is considered to be the weight in the projected area from above and is 0.01 to 5.0 g / m. ² is preferable, and more preferably 0.05 to 1.0 g / m ² . When the amount of the tetraphenylnaphthalocyanine compound of the general formula (1) is less than 0.01 g / m ² , the heat ray shielding effect is reduced, and when it exceeds 5.0 g / m ² , visible light is transmitted. May decrease.

  In addition to the tetraphenylnaphthalocyanine compound represented by the general formula (1), the heat ray shielding material of the present invention may contain various additives used in producing a normal transparent resin material. Examples of the additive include a colorant, a polymerization regulator, an antioxidant, an ultraviolet absorber, a heat ray shielding agent, a flame retardant, a plasticizer, a rubber for improving impact resistance, and a release agent. it can. The heat ray shielding agent means particles capable of absorbing infrared rays having a wavelength of 780 nm or more, and includes aluminum-doped tin oxide, indium-doped tin oxide, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and aluminum. In addition to metal oxides such as doped zinc oxide (AZO), tungsten oxide, composite tungsten oxide, and the like can be given. In particular, tin-doped indium oxide (ITO) is preferable.

The addition amount of the additive in the heat ray shielding agent is not particularly limited, but is usually 10% by weight or less in the heat ray shielding material.
In particular, when the heat ray shielding material of the present invention is used for sunlight, it is a preferable aspect to contain an ultraviolet absorber. It does not restrict | limit especially as a ultraviolet absorber, A well-known ultraviolet absorber can be used. Specifically, salicylic acid, benzophenone, benzotriazole, and cyanoacrylate compounds are preferably used.

In addition to the tetraphenylnaphthalocyanine compound of the general formula (1), the heat ray shielding material of the present invention may contain other near infrared ray absorbing materials. Other near-infrared absorbing materials are not particularly limited, and known near-infrared absorbing materials can be appropriately selected depending on the maximum absorption wavelength desired depending on the application.
In the present invention, the shape of the heat ray shielding material is not particularly limited, and includes various shapes such as a corrugated plate shape, a spherical shape, and a dome shape in addition to the most common flat plate shape and film shape.

  When the heat ray shielding material of the present invention is in the form of a flat plate or a film, the tetraphenylnaphthalocyanine compound of the general formula (1) is mixed with the resin and, if necessary, the additive and other near infrared absorbing materials and then molded. Thus, a heat ray shielding material is obtained. The molding method is not particularly limited, and a known molding method can be applied. Specific examples include extrusion molding, injection molding, cast polymerization, press molding, calender molding, or cast film forming method.

When the use form of the heat ray shielding material of the present invention is a form in which a film containing a tetraphenylnaphthalocyanine compound of the general formula (1) and a resin as essential components is applied on a base material, It can be applied by sticking a film or sheet-like heat ray shielding material using an agent, an adhesive, an adhesive film, or the like. Alternatively, a heat ray shielding material in the form of a film or a sheet can be applied to the substrate by hot pressing or hot lamination molding.
When the usage form of the heat ray shielding material of the present invention is a form in which a coating film containing a tetraphenylnaphthalocyanine compound of the general formula (1) and a resin as essential components is applied on a substrate, the general formula (1) By preparing a coating material (liquid or pasty material) containing a tetraphenylnaphthalocyanine compound and a resin and, if necessary, a solvent for dissolving them and other components, and coating the coating material on the substrate Can be applied.

  The use form of the heat ray shielding material of the present invention is a laminate in which a film containing a tetraphenylnaphthalocyanine compound of the general formula (1) and a resin as essential components is provided as an intermediate layer between two or more substrates For example, a film containing the tetraphenylnaphthalocyanine compound of the general formula (1) and the resin as essential components is sandwiched between the base materials, put into a rubber pack, heated under vacuum and vacuum bonded. Can be applied. Alternatively, a film containing a tetraphenylnaphthalocyanine compound of the general formula (1) and a resin as essential components is sandwiched between the substrates, or on one substrate, the tetraphenylnaphthalocyanine of the general formula (1) Apply a compound and resin, and if necessary, a solvent that dissolves them and a paint containing other components, then place the other base material and apply these laminates by heat or other means. You can also. Furthermore, an adhesive containing a tetraphenylnaphthalocyanine compound of general formula (1) and a resin, or a composition containing a tetraphenylnaphthalocyanine compound of general formula (1) and a resin as an adhesive, It is also possible to apply by bonding.

  Although there is no restriction | limiting in particular as a use of the heat ray shielding material of this invention, The film used for a building, the window of a motor vehicle, etc. as a sun ray heat ray shielding, a sun visor, a goggle for welding, etc. are mentioned. In particular, the tetraphenyl naphthalocyanine compound represented by the general formula (1) of the present invention is excellent in solvent solubility and compatibility with a resin, and in various properties such as heat resistance, light resistance, and weather resistance. It is suitable as a film or an intermediate film used for a window of a building or an automobile.

[Heat ray shielding film]
The case where the heat ray shielding material of the present invention is a heat ray shielding film used by being attached to a window glass or the like of a building will be described below.
Although there is no restriction | limiting in particular as a structure of a heat ray shielding film, For example, the following examples are mentioned.
1. Embodiment 2 which is a film containing a tetraphenylnaphthalocyanine compound of general formula (1) and a resin Aspect 3, which is a mode having a film containing a tetraphenylnaphthalocyanine compound of general formula (1) and a resin, a pressure-sensitive adhesive layer, and a release sheet provided on the surface of the pressure-sensitive adhesive layer as necessary. 3. A mode in which a layer containing a tetraphenylnaphthalocyanine compound of general formula (1) and a resin is provided on a substrate. 4. A mode having a layer containing a tetraphenylnaphthalocyanine compound of general formula (1) and a resin as a pressure-sensitive adhesive on a substrate, and a release sheet provided on the surface of the pressure-sensitive adhesive layer as necessary. Aspects having a substrate, a layer containing a tetraphenylnaphthalocyanine compound of the general formula (1) and a resin, a pressure-sensitive adhesive layer, and a release sheet provided on the surface of the pressure-sensitive adhesive layer as necessary. An aspect having an adhesive layer is preferred from the standpoint of easy attachment to a window glass, and in particular 4. Or 5. This embodiment is preferred.
In addition to these embodiments, further layers such as a hard coat layer, an antifouling layer, an ultraviolet absorbing layer, and an antireflection layer may be provided depending on the purpose.

  Examples of the resin contained together with the tetraphenylnaphthalocyanine compound of the general formula (1) include the same resins as the examples of the resin contained in the heat ray shielding material. In particular, polycarbonate resin, (meth) acrylic resin, polyvinyl resin, polyolefin resin, polybutyral resin, polyester resin, polyamide resin, and polyurethane resin are preferable.

  Examples of the substrate include those similar to the examples of the substrate described in the use form of the heat ray shielding material, but a resin sheet or plate is preferable. Examples thereof include films of polyester, polyethylene, polypropylene, nylon, polyvinyl chloride, polycarbonate, polyvinyl alcohol, polymethyl methacrylate, fluororesin, ethylene, vinyl alcohol resin, and the like. Among these, a polyester film is preferable, and a polyethylene terephthalate (PET) film is more preferable.

The pressure-sensitive adhesive is not particularly limited as long as it can be adhered to a substrate and has transparency. For example, (meth) acrylic type; (meth) acrylic urethane type; (meth) acrylic silicone type; siloxane bond Thermoplastic or thermosetting resins such as polyvinyl chloride, melamine, urethane, styrene, alkyd, phenol, epoxy, polyester, and fluororesin such as polyvinylidene fluoride , Active energy ray-curable curable resin adhesive, natural rubber, butyl rubber, isopropylene rubber, ethylene propylene rubber, methyl rubber, chloroprene rubber, ethylene-propylene copolymer rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, etc. System adhesives and the like.
Examples of the resin that is a pressure-sensitive adhesive include the above-mentioned thermoplastic, thermosetting, and active energy ray-curable curable resin pressure-sensitive adhesives, but (meth) acrylic resins are preferable, and the glass transition temperature is less than 0 ° C. Poly (meth) acrylic acid ester resins are particularly preferred. As poly (meth) acrylic acid ester resin, what uses 50 weight% or more of (meth) acrylic acid ester which has a C1-C14 alkyl group as a monomer is preferable.

Examples of copolymerizable monomers include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate and the like ( (Meth) acrylates; styrene monomers represented by α-methylstyrene, vinyltoluene, styrene, etc .; vinyl ether monomers represented by methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, etc .; fumaric acid, fumaric acid Monoalkyl ester, dialkyl ester of fumaric acid; maleic acid, monoalkyl ester of maleic acid, dialkyl ester of maleic acid, itaconic acid, monoalkyl ester of itaconic acid, dialkyl ester of itaconic acid, (meth) Acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl ketones, vinyl pyridine, and vinyl carbazole.
As the curing agent for the acrylic adhesive, an isocyanate curing agent, an epoxy curing agent, a metal chelate curing agent, or the like is used.

Each layer of the heat ray shielding film may contain the same additives as those used in the production of the heat ray shielding material. Examples include colorants, polymerization regulators, antioxidants, light stabilizers, ultraviolet absorbers, flame retardants, antistatic agents, plasticizers, and the like. In particular, an embodiment containing an ultraviolet absorber is preferred, such as an antioxidant, a flame retardant, an adhesive strength modifier, a moisture-resistant agent, a fluorescent brightening agent, and an infrared absorber.
In addition, a material that can absorb heat rays, such as carbon black, may be used in combination as long as the visible light transmittance is not significantly reduced.
The thickness of the heat ray shielding film varies depending on the configuration, the type of the base material and the resin of the heat ray shielding layer, the use thereof, and the like, but generally a thickness of about 10 μm to 500 μm is preferably used.
For example, when the heat ray shielding film is an embodiment in which a layer containing a tetraphenylnaphthalocyanine compound of the general formula (1) and a resin is provided on the base material, the thickness of the base material is preferably about 20 μm to 300 μm. . The thickness of the layer containing the tetraphenylnaphthalocyanine compound of general formula (1) and the resin is preferably about 0.3 to 100 μm.
The content of the tetraphenylnaphthalocyanine compound of the general formula (1) relative to the resin depends on the thickness of the layer containing the tetraphenylnaphthalocyanine compound of the general formula (1) and the resin. On the other hand, the tetraphenylnaphthalocyanine compound of the general formula (1) is preferably in the range of 0.001 to 30 parts by weight, and more preferably in the range of 0.01 to 10 parts by weight.

As a method for producing the heat ray shielding film of the present invention, after mixing with the tetraphenylnaphthalocyanine compound of general formula (1) and a resin, and if necessary, the above additives, other near infrared absorbers, ultraviolet absorbers, etc. Mold. The molding method is not particularly limited, and a known molding method can be applied as it is or appropriately modified. Specifically, extrusion molding, injection molding, cast polymerization, press molding, calender molding, cast film formation, or the like can be suitably used.
Furthermore, a resin film containing the tetraphenylnaphthalocyanine compound of the general formula (1) can be produced, and the film can be produced by hot pressing or heat laminating the resin material. It can also be produced by printing or coating an acrylic resin ink or paint containing a tetraphenylnaphthalocyanine compound of the general formula (1) on a resin material.

[Interlayer film for laminated glass]
The case where the heat ray shielding material of the present invention is an interlayer film for laminated glass used for automobile window glass and the like will be described below.
The interlayer film for laminated glass is a resin film used in a form sandwiched between two sheets of glass. When the heat ray shielding material of the present invention is an interlayer film for laminated glass, tetraphenyl of the general formula (1) is used. A naphthalocyanine compound and a resin are contained as essential components.
The resin is not particularly limited as long as it has sufficient visibility when used for laminated glass, and preferably has a visible light transmittance of 70% or more when laminated glass is used. For example, polyvinyl acetal resins, polyvinyl chloride resins, saturated polyester resins, polyurethane resins, ethylene-vinyl acetate copolymer resins, ethylene-ethyl acrylate copolymer resins, and the like have been used for intermediate films. The thermoplastic resin which is mentioned. In particular, a plasticized polyvinyl acetal resin is preferable.
As a polyvinyl acetal resin, a polyvinyl formal resin obtained by reacting polyvinyl alcohol (PVA) and formaldehyde, a narrowly defined polyvinyl acetal resin obtained by reacting PVA and acetaldehyde, PVA and n-butyraldehyde are reacted. The polyvinyl butyral resin (PVB) etc. which are obtained by making it include are mentioned, and especially a polyvinyl butyral resin (PVB) is preferable.
The PVA used for the synthesis of the polyvinyl acetal resin preferably has an average degree of polymerization of 200 to 5000, more preferably 500 to 3000. The polyvinyl acetal resin preferably has a degree of acetalization of 40 to 85 mol%, more preferably 50 to 75 mol%. Moreover, the thing whose residual acetyl group amount is 30 mol% or less is preferable, More preferably, it is a thing of 0.5-24 mol%.

Examples of the plasticizer used for plasticizing a thermoplastic resin, preferably a polyvinyl acetal resin, include, for example, organic acid ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, Examples thereof include phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid.
The thickness of the interlayer film for laminated glass varies depending on the type of resin, its use, etc., but is usually preferably in the range of 0.1 to 3 mm, and in the range of 0.3 mm to 1.5 mm. More preferably.
The content of the tetraphenylnaphthalocyanine compound of the general formula (1) with respect to the resin is not particularly limited, but the tetraphenylnaphthalocyanine compound of the general formula (1) is within the range of 0.001 to 2 parts by weight with respect to 100 parts by weight of the resin. It is preferable that it is in the range of 0.005 to 0.5 parts by weight.
The interlayer film for laminated glass of the present invention may contain the same additives as those used in the production of the heat ray shielding material. For example, a heat ray shielding agent, an ultraviolet absorber, an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, an adhesive force adjusting agent, a moisture resistant agent, a fluorescent brightening agent, a colorant, an infrared absorber, and the like can be given. In particular, an embodiment containing an ultraviolet absorber is preferable.

Examples of the method for producing the interlayer film for laminated glass of the present invention include the same methods as those for producing the heat ray shielding material and the heat ray shielding film. The interlayer film for laminated glass according to the present invention has at least one of a primer function, an ultraviolet cut function, a flame retardant function, an antireflection function, an antiglare function, an antireflection antiglare function, and an antistatic function as necessary. It is good also as a multilayer structure combined with the functional transparent layer which has a function. The laminated glass using the interlayer film for laminated glass of the present invention has a configuration in which the interlayer film of the present invention is sandwiched and bonded and integrated between at least two transparent glass substrates.
Although it does not specifically limit as a transparent glass base material, For example, float plate glass, polished plate glass, flat glass, curved plate glass, parallel plate glass, type plate glass, wire mesh type plate glass, heat ray absorption plate glass, clear glass, colored glass plate, etc. And various inorganic glass plates, organic glass plates such as polycarbonate plates and polymethyl methacrylate plates. These transparent glass substrates may be used alone or in combination of two or more kinds.
As a method for producing a laminated glass, for example, the interlayer film of the present invention is sandwiched between two transparent glass substrates and put in a vacuum bag, and the pressure in the vacuum bag is about −65 to −100 kPa. After preliminarily adhering at a temperature of about 70 to 110 ° C. while suctioning at a reduced pressure so that the pressure is within the range, the pressure inside the autoclave is further reduced by suction so that the pressure in the autoclave is about 0.98 to 1.47 MPa. It can be obtained by performing the main adhesion at a temperature of about 120 to 150 ° C.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
[Example 1] Production of 1- (3,5-difluorophenyl) naphthalene-2,3-dicarbonitrile (specific example (2) -11) 19 g of 3,5-difluoro-2'-methylbenzophenone and N- 16.6 g of bromosuccinimide and 0.5 g of radical generator V-70 (an azonitrile compound manufactured by Wako Pure Chemical Industries, Ltd.) were stirred at an internal temperature of 70 ° C. in 60 mL of benzene for 2 hours.
After cooling, succinimide was removed by filtration, 7.93 g of fumaronitrile was added, and the mixture was stirred at an internal temperature of 90 ° C. for 16 hours.
The reaction solution was cooled to 0 ° C., 20 mL of concentrated sulfuric acid was added dropwise, stirred for 10 minutes, the benzene solution was washed with water, and the solvent was distilled off by an evaporator and dried.
Subsequently, the obtained solid was purified by column chromatography (silica gel / chloroform) to obtain 12.5 g of a white solid (melting point: 182 ° C.). The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 290 (M +)
IR: νCN: 2231 cm ⁻¹
・ Elemental analysis values:
Measured value (C: 74.52%, H: 2.81%, N: 9.60%);
Theoretical value (C: 74.48%, H: 2.78%, N: 9.65%)
・¹ H NMR δ 6.96-7.02 (m, 2H), 7.06 (tt, J = 2.3 and 8.7 Hz, 1H), 7.69 (d, J = 8.2 Hz, 1H), 7.75 (dt, J = 1.4 and 7.7 Hz , 1H), 7.82 (dt, J = 1.4 and 7.7 Hz, 1H), 8.05 (d, J = 7.8 Hz, 1H), 8.42 (s, 1H)
The H-NMR spectrum is shown in FIG.

[Example 2] Production of 6-t-butyl-1- (3,5-difluorophenyl) naphthalene-2,3-dicarbonitrile (specific example (2) -18) 3,5-difluoro-2'- Methyl-4′-t-butylbenzophenone (21.2 g), N-bromosuccinimide (14.4 g), and radical generator V-70 (0.5 g) were stirred in benzene (40 mL) at an internal temperature of 70 ° C. for 2 hours.
After cooling, succinimide was removed by filtration, 6.25 g of fumaronitrile was added, and the mixture was stirred at an internal temperature of 90 ° C. for 16 hours.
The reaction solution was cooled to 0 ° C., 20 mL of concentrated sulfuric acid was added dropwise, stirred for 10 minutes, the benzene solution was washed with water, and the solvent was distilled off by an evaporator and dried.
Next, the obtained solid was purified by column chromatography (silica gel / chloroform) to obtain 13.4 g of a white solid (melting point: 167 ° C.). The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 346 (M +)
IR: νCN: 2229 cm ⁻¹
・ Elemental analysis values:
Measured value (C: 76.32%, H: 4.69%, N: 8.03%);
Theoretical value (C: 76.29%, H: 4.66%, N: 8.09%)
・¹ H NMR δ 1.42 (s, 9H), 6.96 (m, 2H), 7.04 (tt, J = 2.4 and 8.8 Hz, 1H), 7.62 (d, J = 9.2 Hz, 1H), 7.77 (dd, J = 2.4 and 8.8 Hz, 1H), 7.93 (d, J = 2.4 Hz, 1H), 8.36 (s, 1H)
The H-NMR spectrum is shown in FIG.

[Example 3] Preparation of 4- (3,5-difluorophenyl) -7-t-butyl-1,3-diiminobenzoisoindoline (specific example (3) -18) 28% sodium methoxide solution After 3 mL of ammonia was blown and saturated, 6 g of 6-tert-butyl-1- (3,5-difluorophenyl) naphthalene-2, 3-dicarbonitrile prepared in Example 2 and 50 mL of toluene were added. Stir at 0 ° C. for 3 hours.
After distilling off the solvent and ammonia, 50 mL of water was added to the distillation residue, dispersed and filtered. The filter paste was washed with water and dried to obtain 5.39 g of a white powder (decomposed at 151 ° C.). The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 363 (M +)
IR: νNH: 1616, 1668 cm ⁻¹
・ Elemental analysis values:
Measured value (C: 73.00%, H: 5.52%, N: 11.51%);
Theoretical value (C: 72.71%, H: 5.27%, N: 11.56%)
・¹ H NMR δ 1.41 (s, 9H), 7.05 (m, 2H), 7.17 (tt, J = 2.4 and 8.8 Hz, 1H), 7.49 (d, J = 8.8 Hz, 1H), 7.68-7.73 (m , 2H), 8.05 (s, 1H), 8.36 (s, 1H)

Example 4 Production of 1- (3,5-bis (trifluoromethyl) phenyl) naphthalene-2,3-dicarbonitrile (specific example (2) -31) 3,5-bis (trifluoromethyl) -2'-methylbenzophenone (27.6 g), N-bromosuccinimide (16.3 g) and radical generator V-70 (0.5 g) were stirred in 60 mL of benzene at an internal temperature of 70 ° C. for 2 hours.
After cooling, succinimide was removed by filtration, 7.78 g of fumaronitrile was added, and the mixture was stirred at an internal temperature of 90 ° C. for 16 hours.
The reaction solution was cooled to 0 ° C., 20 mL of concentrated sulfuric acid was added dropwise, stirred for 10 minutes, the benzene solution was washed with water, and the solvent was distilled off by an evaporator and dried.
Subsequently, the obtained solid was purified by column chromatography (silica gel / chloroform) to obtain 14.6 g of a white solid (melting point: 245 ° C.). The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 390 (M +)
IR: νCN: 2231 cm ⁻¹
・ Elemental analysis values:
Measured value (C: 61.58%, H: 2.11%, N: 7.13%);
Theoretical value (C: 61.55%, H: 2.07%, N: 7.18%)
¹ H NMR δ 7.57 (d, J = 8.2 Hz, 1H), 7.79 (dt, J = 1.4 and 8.7 Hz, 1H), 7.86 (dt, J = 1.4 and 8.2 Hz, 1H), 7.94 (s, 2H ), 8.12 (d, J = 1.8 Hz, 1H), 8.14 (s, 1H), 8.47 (s, 1H)
The H-NMR spectrum is shown in FIG.

Example 5 Production of 6-t-butyl-1- (3,5-bis (trifluoromethyl) phenyl) naphthalene-2,3-dicarbonitrile (specific example (2) -38) Bis (trifluoromethyl) -2′-methyl-4′-t-butylbenzophenone (8.04 g), N-bromosuccinimide (4.18 g) and radical generator V-70 (0.2 g) in benzene (15 mL) at an internal temperature of 70 ° C. Stir for 2 hours.
After cooling, succinimide was removed by filtration, 4.57 g of fumaronitrile was added, and the mixture was stirred at an internal temperature of 90 ° C. for 16 hours.
The reaction solution was cooled to 0 ° C., 10 mL of concentrated sulfuric acid was added dropwise, and the mixture was stirred for 10 minutes. The benzene solution was washed with water, and the solvent was distilled off with an evaporator and dried.
Subsequently, the obtained solid was purified by column chromatography (silica gel / chloroform) to obtain 4.57 g of a white solid (melting point: 248 ° C.). The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 446 (M +)
IR: νCN: 2233 cm ⁻¹
・ Elemental analysis values:
Measured value (C: 64.63%, H: 3.65%, N: 6.23%);
Theoretical value (C: 64.58%, H: 3.61%, N: 6.28%)
・¹ H NMR δ 1.43 (s, 9H), 7.48 (d, J = 9.1 Hz, 1H), 7.84 (dd, J = 2.3 and 8.8 Hz, 1H), 7.91 (s, 2H), 7.97 (d, J = 1.8 Hz, 1H), 8.11 (s, 1H), 8.41 (s, 1H)

Example 6 Production of 4- (3,5-bis (trifluoromethyl) phenyl) -7-t-butyl-1,3-diiminobenzoisoindoline (specific example (3) -38)
Ammonia was blown into 6.3 mL of a 28% sodium methoxide solution to saturate, and then 6 g of 1- (3,5-difluorophenyl) -6-fluoronaphthalene-2,3-dicarbonitrile prepared in Example 5 and Toluene 50mL was added and it stirred at 60 degreeC for 3 hours.
After distilling off the solvent and ammonia, 50 mL of water was added to the distillation residue, dispersed and filtered. The filter paste was washed with water and dried to obtain 5.39 g of a white powder (decomposed at 173 ° C.). The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 463 (M +)
IR: νNH: 1618, 1666 cm ⁻¹
・ Elemental analysis values:
Measured value (C: 62.46%, H: 4.26%, N: 9.21%);
Theoretical value (C: 62.20%, H: 4.13%, N: 9.07%)
・¹ H NMR δ 1.42 (s, 9H), 7.32 (d, J = 9.2 Hz, 1H), 7.66 (m, 2H), 7.92 (s, 1H), 7.99 (s, 1H), 8.10 (s, 1H ), 8.33 (s, 1H)

[Example 7] Production of 1- (3,5-bis (trifluoromethyl) phenyl) -6-fluoronaphthalene-2,3-dicarbonitrile (specific example (2) -33) 3,5-bis ( Trifluoromethyl) -2′-methyl-6-fluorobenzophenone 35 g, N-chlorosuccinimide 32.68 g and radical generator V-65 1.2 g were stirred in chlorobenzene 80 mL at an internal temperature of 70 ° C. for 33 hours.
After cooling, succinimide was removed by filtration, 7.8 g of fumaronitrile was added, and the mixture was stirred at an internal temperature of 130 ° C. for 11 hours.
The reaction solution was cooled to 0 ° C., 12 mL of concentrated sulfuric acid was added dropwise, stirred for 10 minutes, the benzene solution was washed with water, and the solvent was distilled off by an evaporator and dried.
Subsequently, the obtained solid was purified by column chromatography (silica gel / heptane) to obtain 12.65 g of a white solid (melting point: 245 ° C.). The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 408 (M +)
IR: νCN: 2235 cm ⁻¹
・ Elemental analysis values:
Measured value (C: 58.81%, H: 1.70%, N: 6.88%);
Theoretical value (C: 58.84%, H: 1.73%, N: 6.86%)
¹ H NMR δ 7.48 (d, J = 9.1 Hz, 1H), 7.55 (dd, J = 2.3 and 8.8 Hz, 1H), 7.59 (d, J = 1.8 Hz, 1H), 7.93 (s, 2H), 8.11 (s, 1H), 8.41 (s, 1H).

[Example 8] Preparation of 4- (3,5-bis (trifluoromethyl) phenyl) -7-fluoro-1,3-diiminobenzoisoindoline (specific example (3) -33) Sodium methoxide 28% Ammonia was blown into 6.3 mL of the solution to saturate, and then 6 g of 1- (3,5-trifluorophenyl) -6-fluoronaphthalene-2,3-dinitrile prepared in Example 7 and 50 mL of toluene were added. Stir at 0 ° C. for 3 hours.
After distilling off the solvent and ammonia, 50 mL of water was added to the distillation residue, dispersed and filtered. The filter paste was washed with water and dried to obtain 5.39 g of a white powder (decomposed at 162 ° C.). The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 426 (M +)
IR: νNH: 2230 cm ⁻¹
・ Elemental analysis values:
Measured value (C: 56.51%, H: 2.40%, N: 9.85%);
Theoretical value (C: 56.48%, H: 2.37%, N: 9.88%)
¹ H NMR δ 7.32 (d, J = 9.1 Hz, 1H), 7.39 (dd, J = 2.3 and 8.8 Hz, 1H), 7.56 (d, J = 1.8 Hz, 1H), 7.94 (s, 2H), 8.09 (s, 1H), 8.38 (s, 1H).

[Example 9] Production of tetraphenylnaphthalocyanine compound (specific example (1) -7)
1.03 g of 1- (3,5-difluorophenyl) naphthalene-2,3-dicarbonitrile prepared in Example 1, 0.17 g of palladium chloride, and 0.5 mL of DBU in 50 mL of 1-dodecanol had an internal temperature of 100 ° C. For 48 hours. After distilling off the solvent with an evaporator, 30 mL of methanol was added, and the precipitate was collected by filtration and dried. Purification by column chromatography (activated alumina / methylene chloride) gave 0.35 g of a dark green powder. The obtained compound was confirmed to be the target compound from the following analysis results.
In addition, the tetraphenyl naphthalocyanine compound of the following Example obtained by this compound and the same manufacturing method is a mixture of each isomer represented by Formula (1) -a- (1) -d.
MS: (EI) m / z 1266 (M +)
・ Elemental analysis values:
Measured value (C: 68.18%, H: 2.70%, N: 8.59%);
Theoretical value (C: 68.23%, H: 2.54%, N: 8.84%)
The toluene solution of the compound thus obtained showed a maximum absorption at 768 nm, and the gram extinction coefficient was 2.10 × 10 ⁵ g / mL · cm. This absorption spectrum chart is shown in FIG.

[Example 10] Production of tetraphenylnaphthalocyanine compound (specific example (1) -8) The same procedure as in Example 9 except that 0.1 g of copper chloride was used instead of 0.17 g of palladium chloride in Example 9. 0.7 g of dark green powder was obtained. The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 1223 (M +)
・ Elemental analysis values:
Measured value (C: 70.63%, H: 2.59%, N: 8.95%);
Theoretical value (C: 70.62%, H: 2.63%, N: 9.15%)
The toluene solution of the compound thus obtained showed a maximum absorption at 793 nm, and the gram extinction coefficient was 1.86 × 10 ⁵ g / mL · cm. This absorption spectrum chart is shown in FIG.

[Example 11] Production of tetraphenylnaphthalocyanine compound (specific example (1) -34) 1- (3,5-bis (trifluoromethyl) phenyl) naphthalene-2,3-dicarbohydrate produced in Example 4 1.02 g of nitrile, 0.12 g of palladium chloride, and 0.5 mL of DBU were stirred in 50 mL of 1-dodecanol at an internal temperature of 100 ° C. for 48 hours.
After distilling off the solvent with an evaporator, 30 mL of methanol was added, and the precipitate was collected by filtration and dried. Purification by column chromatography (activated alumina / methylene chloride) gave 0.3 g of a dark green powder. The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 1665 (M +)
・ Elemental analysis values:
Measured value (C: 57.65%, H: 2.18%, N: 6.52%);
Theoretical value (C: 57.62%, H: 1.93%, N: 6.72%)
The ¹ H NMR spectrum in deuterated chloroform is shown in FIG.
The toluene solution of the compound thus obtained showed a maximum absorption at 753 nm, and the gram extinction coefficient was 1.95 × 10 ⁵ g / mL · cm. This absorption spectrum chart is shown in FIG.

[Example 12] Production of tetraphenylnaphthalocyanine compound (specific example (1) -36) The same procedure as in Example 11 except that 0.07 g of copper chloride was used instead of 0.12 g of palladium chloride in Example 11. 0.5 g of dark green powder was obtained. The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 1623 (M +)
・ Elemental analysis values:
Measured value (C: 59.30%, H: 1.79%, N: 6.90%);
Theoretical value (C: 59.14%, H: 1.99%, N: 6.90%)
The toluene solution of the compound thus obtained showed a maximum absorption at 778 nm, and the gram extinction coefficient was 1.63 × 10 ⁵ g / mL · cm. This absorption spectrum chart is shown in FIG.

[Example 13] Production of tetraphenylnaphthalocyanine compound (specific example (1) -26) 4- (3,5-difluorophenyl) -7-t-butyl-1,3-diimino produced in Example 3 1 g of benzoisoindoline, 0.16 g of palladium chloride, and 1 mL of DBU were stirred in 40 mL of n-butanol at an internal temperature of 100 ° C. for 36 hours. After distilling off the solvent with an evaporator, 30 mL of methanol was added, and the precipitate was collected by filtration and dried. Purification by column chromatography (activated alumina / methylene chloride) gave 0.6 g of a dark green powder. The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 1490 (M +)
・ Elemental analysis values:
Measured value (C: 70.95%, H: 4.63%, N: 7.17%);
Theoretical value (C: 70.84%, H: 4.32%, N: 7.51%)
The toluene solution of the compound thus obtained showed a maximum absorption at 767 nm, and the gram extinction coefficient was 1.95 × 10 ⁵ g / mL · cm. This absorption spectrum chart is shown in FIG.

[Example 14] Production of tetraphenylnaphthalocyanine compound (specific example (1) -27) The same procedure as in Example 13 except that 0.09 g of copper chloride was used instead of 0.16 g of palladium chloride in Example 13. 0.7 g of dark green powder was obtained. The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 1447 (M +)
・ Elemental analysis values:
Measured value (C: 73.01%, H: 4.81%, N: 7.89%);
Theoretical value (C: 72.94%, H: 4.45%, N: 7.73%)
The toluene solution of the compound thus obtained showed a maximum absorption at 793 nm, and the gram extinction coefficient was 1.57 × 10 ⁵ g / mL · cm. This absorption spectrum chart is shown in FIG.

[Example 15] Production of tetraphenylnaphthalocyanine compound (specific example (1) -29) The same procedure as in Example 13 except that 0.14 g of vanadium chloride was used instead of 0.16 g of palladium chloride in Example 13. 0.8 g of dark green powder was obtained. The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 1451 (M +)
・ Elemental analysis values:
Measured value (C: 73.03%, H: 4.81%, N: 7.49%);
Theoretical value (C: 72.77%, H: 4.44%, N: 7.71%)
The toluene solution of the compound thus obtained showed a maximum absorption at 818 nm, and the gram extinction coefficient was 1.73 × 10 ⁵ g / mL · cm. This absorption spectrum chart is shown in FIG.

[Example 16] Production of tetraphenylnaphthalocyanine compound (specific example (1) -37) 4- (3,5-bis (trifluoromethyl) phenyl) -7-t-butyl-1 produced in Example 6 , 3-Diiminobenzoisoindoline 1.12 g, palladium chloride 0.12 g and DBU 1 mL were stirred in 80 mL of n-butanol at an internal temperature of 100 ° C. for 36 hours. After distilling off the solvent with an evaporator, 30 mL of methanol was added, and the precipitate was collected by filtration and dried. Purification by column chromatography (activated alumina / methylene chloride) gave 0.6 g of a dark green powder. The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 1889 (M +)
・ Elemental analysis values:
Measured value (C: 61.26%, H: 3.67%, N: 5.79%);
Theoretical value (C: 60.94%, H: 3.41%, N: 5.92%)
The toluene solution of the compound thus obtained showed a maximum absorption at 780 nm, and the gram extinction coefficient was 2.06 × 10 ⁵ g / mL · cm. This absorption spectrum chart is shown in FIG.
This compound is a mixture of isomers represented by the general formulas (1) -a to (1) -d. The mixture was further subjected to column chromatography as described below to separate each fraction, thereby separating each isomer.
110 mg of this compound (mixture) was subjected to silica gel column chromatography (hexane / chloroform 8/1, v / v) to fractionate each fraction. Each obtained fraction was concentrated with an evaporator, an appropriate amount of hexane was added, and the mixture was stirred and the precipitate was filtered and dried. In addition, the fraction of the isomer corresponding to the general formula (1) -d was very small and could not be isolated.
26 mg of the isomer of (1) -37-a having an Rf value of 0.74, 14 mg of the isomer of (1) -37-b having an Rf value of 0.55, and (1) -37-c having an Rf value of 0.37 16 mg of each isomer was isolated.

・ＭＳ：（ＥＩ）ｍ/z １８８９（Ｍ＋）
・元素分析値：
実測値（Ｃ：６１．２１％、Ｈ：３．４７％、Ｎ：５．８１％）；
理論値（Ｃ：６０．９４％、Ｈ：３．４１％、Ｎ：５．９２％）
・¹Ｈ−ＮＭＲ δ 1.66 (s, 36H), 7.90-7.99 (m, 8H), 8.37 (s, 4H), 8.48 (s, 8H), 8.57 (s, 4H), 8.66 (s, 4H)
重クロロホルム中の^１Ｈ−ＮＭＲスペクトルを図１３に示す。
・単結晶Ｘ線回折測定による構造解析（分析装置：Rigaku AFC―7 Mercury
CCD area detector）

MS: (EI) m / z 1889 (M +)
・ Elemental analysis values:
Measured value (C: 61.21%, H: 3.47%, N: 5.81%);
Theoretical value (C: 60.94%, H: 3.41%, N: 5.92%)
・¹ H-NMR δ 1.66 (s, 36H), 7.90-7.99 (m, 8H), 8.37 (s, 4H), 8.48 (s, 8H), 8.57 (s, 4H), 8.66 (s, 4H)
A ¹ H-NMR spectrum in deuterated chloroform is shown in FIG.
・ Structural analysis by single crystal X-ray diffraction measurement (analyzer: Rigaku AFC-7 Mercury
CCD area detector)

The single crystal used for the X-ray crystal structure analysis was produced by a diffusion method in a mixed solvent system using chloroform as a good solvent and methanol as a poor solvent.
For the reflection intensity measurement, a Rigaku Mercury single crystal X-ray structural analysis device with a CCD detector using Mo-Kα rays (λ = 0.71075 mm) monochromatized with graphite as the light source, 20 ± 1 ° C., 2θ Measurements were made in the range up to 62.5 °.
The Crystal Structure crystal structure analysis program package was used for calculations related to structural analysis. The structure was determined using reflection of I> 2.00σ (I), and an approximate structure was obtained by a direct method using an SIR92 analysis program and a Fourier diagram using a DIRDIF99 analysis program. The final structural refinement was performed by the full matrix least squares method. In addition, atoms other than hydrogen were refined using an anisotropic temperature factor, and the coordinates of hydrogen atoms were obtained by calculation. Since disorder was found for each of the fluorine atoms of the eight trifluoromethyl groups, the occupation ratio of each fluorine atom was refined to 50%.

・ＭＳ：（ＥＩ）ｍ/z １８８９（Ｍ＋）
・元素分析値：
実測値（Ｃ：６１．３２％、Ｈ：３．４０％、Ｎ：５．８０％）；
理論値（Ｃ：６０．９４％、Ｈ：３．４１％、Ｎ：５．９２％）
・¹Ｈ−ＮＭＲ δ 1.58 (s, 9H), 1.59 (s, 9H), 1.64(s, 9H), 1.66(s, 9H), 7.67-8.05(m, 20H), 8.17-8.20 (m, 10H), 8.38-8.70 (m, 22H), 10.11 (s, 4H)
重クロロホルム中の^１Ｈ−ＮＭＲスペクトルを図１４に示す。

MS: (EI) m / z 1889 (M +)
・ Elemental analysis values:
Measured value (C: 61.32%, H: 3.40%, N: 5.80%);
Theoretical value (C: 60.94%, H: 3.41%, N: 5.92%)
・¹ H-NMR δ 1.58 (s, 9H), 1.59 (s, 9H), 1.64 (s, 9H), 1.66 (s, 9H), 7.67-8.05 (m, 20H), 8.17-8.20 (m, 10H ), 8.38-8.70 (m, 22H), 10.11 (s, 4H)
The ¹ H-NMR spectrum in deuterated chloroform is shown in FIG.

・ＭＳ：（ＥＩ）ｍ/z １８８９（Ｍ＋）
・元素分析値：
実測値（Ｃ：６０．９２％、Ｈ：３．３７％、Ｎ：５．７９％）；
理論値（Ｃ：６０．９４％、Ｈ：３．４１％、Ｎ：５．９２％）
・¹Ｈ−ＮＭＲ δ 1.60 (s, 18H), 1.64 (s, 18H) , 7.67-8.02 (m, 20H), 8.12-8.20 (m, 12H), 8.41-8.68 (m, 20H), 10.12 (s, 4H);
重クロロホルム中の^１Ｈ−ＮＭＲスペクトルを図１５に示す。

MS: (EI) m / z 1889 (M +)
・ Elemental analysis values:
Measured value (C: 60.92%, H: 3.37%, N: 5.79%);
Theoretical value (C: 60.94%, H: 3.41%, N: 5.92%)
・¹ H-NMR δ 1.60 (s, 18H), 1.64 (s, 18H), 7.67-8.02 (m, 20H), 8.12-8.20 (m, 12H), 8.41-8.68 (m, 20H), 10.12 (s , 4H);
A ¹ H-NMR spectrum in deuterated chloroform is shown in FIG.

[Example 17] Production of tetraphenylnaphthalocyanine compound (specific example (1) -41) The same procedure as in Example 16 except that 0.07 g of copper chloride was used instead of 0.12 g of palladium chloride in Example 16. 0.7 g of dark green powder was obtained. The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 1848 (M +)
・ Elemental analysis values:
Measured value (C: 62.23%, H: 3.71%, N: 6.00%);
Theoretical value (C: 62.36%, H: 3.49%, N: 6.06%)
The toluene solution of the compound thus obtained showed a maximum absorption at 780 nm, and the gram extinction coefficient was 1.67 × 10 ⁵ g / mL · cm. This absorption spectrum chart is shown in FIG.
This compound is a mixture of isomers represented by the general formulas (1) -a to (1) -d. The mixture was further subjected to column chromatography as described below to separate each isomer.
110 mg of this compound (mixture) was subjected to silica gel column chromatography (hexane / chloroform 8/1, v / v) to fractionate each fraction. Each obtained fraction was concentrated with an evaporator, an appropriate amount of hexane was added, and the mixture was stirred and the precipitate was filtered and dried. 64 mg of isomer of (1) -41-a with Rf value of 0.75, 12 mg of isomer of (1) -41-b with Rf value of 0.55, (1) -41-c of Rf value of 0.37 Each 13 mg of isomers was isolated. In addition, the fraction of the isomer corresponding to the general formula (1) -d was very small and could not be isolated.

・ＭＳ：（ＥＩ）ｍ/z １８４８（Ｍ＋）
・元素分析値：
実測値（Ｃ：６２．２４％、Ｈ：３．５８％、Ｎ：６．０３％）；
理論値（Ｃ：６２．３６％、Ｈ：３．４９％、Ｎ：６．０６％）
この化合物のトルエン溶液は７８０ｎｍに極大吸収を示し、グラム吸光係数は１．７５×１０^５ｇ/ｍＬ・ｃｍであった。

MS: (EI) m / z 1848 (M +)
・ Elemental analysis values:
Measured value (C: 62.24%, H: 3.58%, N: 6.03%);
Theoretical value (C: 62.36%, H: 3.49%, N: 6.06%)
The toluene solution of this compound showed a maximum absorption at 780 nm, and the gram extinction coefficient was 1.75 × 10 ⁵ g / mL · cm.

・ＭＳ：（ＥＩ）ｍ/z １８４８（Ｍ＋）
・元素分析値：
実測値（Ｃ：６２．２８％、Ｈ：３．５３％、Ｎ：６．０４％）；
理論値（Ｃ：６２．３６％、Ｈ：３．４９％、Ｎ：６．０６％）

MS: (EI) m / z 1848 (M +)
・ Elemental analysis values:
Measured value (C: 62.28%, H: 3.53%, N: 6.04%);
Theoretical value (C: 62.36%, H: 3.49%, N: 6.06%)

・ＭＳ：（ＥＩ）ｍ/z １８４８（Ｍ＋）
・元素分析値：
実測値（Ｃ：６２．３９％、Ｈ：３．５２％、Ｎ：６．０５％）；
理論値（Ｃ：６２．３６％、Ｈ：３．４９％、Ｎ：６．０６％）

MS: (EI) m / z 1848 (M +)
・ Elemental analysis values:
Measured value (C: 62.39%, H: 3.52%, N: 6.05%);
Theoretical value (C: 62.36%, H: 3.49%, N: 6.06%)

[Example 18] Production of tetraphenylnaphthalocyanine compound (specific example (1) -35) The same procedure as in Example 16 except that 0.11 g of vanadium chloride was used instead of 0.12 g of palladium chloride in Example 16. 0.8 g of dark green powder was obtained. The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 1851 (M +)
・ Elemental analysis values:
Measured value (C: 62.21%, H: 3.66%, N: 5.83%);
Theoretical value (C: 62.24%, H: 3.48%, N: 6.05%)
The toluene solution of the compound thus obtained showed a maximum absorption at 818 nm, and the gram extinction coefficient was 1.73 × 10 ⁵ g / mL · cm. This absorption spectrum chart is shown in FIG.

[Example 19] Production of tetraphenylnaphthalocyanine compound (specific example (1) -64)
1- (3,5-bis (trifluoromethylphenyl) -6-fluoronaphthalene-2,3-dicarbonitrile prepared in Example 7 (4.0 g), copper chloride (0.339 g), DBU (1 mL) was added to n-octanol (25 mL). The mixture was stirred for 5 hours at an internal temperature of 180 ° C. After evaporation of the solvent with an evaporator, 30 mL of methanol was added, the precipitate was collected by filtration and dried, and purified by column chromatography (silica gel / toluene). 1.0 g of powder was obtained, and the obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 1695 (M +)
・ Elemental analysis values:
Measured value (C: 56.81%, H: 1.66%, N: 6.83%);
Theoretical value (C: 56.63%, H: 1.66%, N: 6.60%)
The toluene solution of the compound thus obtained showed a maximum absorption at 771 nm, and the gram extinction coefficient was 1.38 × 10 ⁵ g / mL · cm. This absorption spectrum chart is shown in FIG.

[Example 20] Production of tetraphenylnaphthalocyanine compound (specific example (1) -65)
Instead of 0.339 g of copper chloride in Example 19, 0.54 g of vanadium chloride, 1- (3,5-bis (trifluoromethylphenyl) -6-fluoronaphthalene-2,3-dicarbox prepared in Example 7 Except that 4.17 g of 4- (3,5-bis (trifluoromethyl) phenyl) -6-fluoro-1,3-diimino-benzoisoindoline synthesized in Example 8 was used instead of 4.0 g of nitrile. 2.1 g of dark green powder was obtained in the same manner as in Example 19. The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 1699 (M +)
・ Elemental analysis values:
Measured value (C: 59.53%, H: 1.93%, N: 3.27%);
Theoretical value (C: 56.52%, H: 1.66%, N: 6.59%)
The toluene solution of the compound thus obtained showed a maximum absorption at 808 nm, and the gram extinction coefficient was 2.09 × 10 ⁵ g / mL · cm. This absorption spectrum chart is shown in FIG.

[Comparative Example 1] Production of tetraphenyl-Pd-naphthalocyanine compound 5 g of 4-phenyl-1,3-diiminobenzoisoindoline, 0.82 g of palladium chloride and 1 mL of DBU in 30 mL of n-octanol at an internal temperature of 200 ° C. And stirred for 3 hours. After distilling off the solvent with an evaporator, 30 mL of methanol was added, and the precipitate was collected by filtration and dried. Purification by column chromatography (activated alumina / methylene chloride) gave 2.1 g of a dark green powder. The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 1121M +)
・ Elemental analysis values:
Measured value (C: 77.01%, H: 3.62%, N: 9.95%);
Theoretical value (C: 76.97%, H: 3.59%, N: 9.97%)
The toluene solution of the compound thus obtained showed a maximum absorption at 770 nm, and the gram extinction coefficient was 2.07 × 10 ⁵ g / mL · cm. This absorption spectrum chart is shown in FIG.

[solubility]
About the tetraphenyl naphthalocyanine compound of this invention manufactured in the said Example and the comparative example compound, the solubility with respect to the organic solvent was measured with the following measuring method. The results are shown in Table 4.

(Solubility measurement method)
Toluene or chloroform was added to about 0.1 g of tetraphenylnaphthalocyanine compound so that the total weight was about 10 g, and the mixture was irradiated with ultrasonic waves for about 30 minutes, and then stirred at room temperature for 2 hours to obtain a dispersion of about 1 wt%. Prepared.
The dispersion was filtered through a membrane filter (0.2 μm), and the obtained filtrate was dried in a dryer at 60 ° C. for 1 hour, and the weight of the filtrate was measured.
The solubility of the tetraphenylnaphthalocyanine compound in the solvent was expressed by the following formula.
Solubility (wt%) = (W0−W1) / W0
W0: exact weight of tetraphenylnaphthalocyanine compound before treatment, W1: weight of filtrate after drying (dissolved residue of tetraphenylnaphthalocyanine compound). If no filter residue remained on the filter, the solubility was 1 wt% or more.

比較例２の化合物（以下「比較例２化合物」と略称）

上記比較例１化合物は、先の比較例 1 にて製造したテトラフェニル-Ｐｄ-ナフタロシアニンである。比較例２化合物は特開２００９−２９９５５に記載の実施例１に従い製造した。All of the compounds of Examples have higher solubility in toluene and chloroform than the compounds of Comparative Examples.
Compound of Comparative Example 1 (hereinafter abbreviated as “Comparative Example 1 Compound”)

Compound of Comparative Example 2 (hereinafter abbreviated as “Comparative Example 2 Compound”)

The compound of Comparative Example 1 is tetraphenyl-Pd-naphthalocyanine prepared in the above Comparative Example 1. Comparative Example 2 The compound was produced according to Example 1 described in JP-A-2009-29955.

[Visible light transmittance]
The visible light transmittances of the tetraphenylnaphthalocyanine compound and the comparative example compound of the present invention were measured by the following measuring method. The results are shown in Tables 5 and 6.
FIG. 21 shows a comparison of transmission spectra of the tetraphenylnaphthalocyanine compound of the present invention produced in Example 15 and Example 20 and the compound of Comparative Example 2.
(Visible light transmittance measurement method)
In a 100 mL volumetric flask, 1.000 mg of each naphthalocyanine compound and about 90 mL of chloroform were placed, irradiated with ultrasonic waves for 30 minutes, and allowed to stand at room temperature for 2 hours. Thereafter, chloroform was added so that the meniscus of the solution coincided with the marked line of the volumetric flask to prepare a 10 mg / L naphthalocyanine solution. The solution thus prepared was placed in a 1 cm square Pyrex (registered trademark) cell, and the absorption spectrum was measured using a spectrophotometer (manufactured by Hitachi, Ltd .: Spectrophotometer U-3500).
From the absorption spectrum measured in this way, as shown in FIG. 21, a conversion spectrum was obtained by converting the absorbance at the absorption maximum wavelength in the near infrared region to 1.0, that is, the transmittance was 10%. . The transmittance of this transmission spectrum at 460 nm and 610 nm is shown in Table 5 for compounds whose central metals are copper and palladium, and in Table 6 for compounds whose central metals are vanadium.
Compared with the compounds of Comparative Example 1 and Comparative Example 2, the compound of the present invention has substantially the same transmittance at 610 nm, but the transmittance at 460 nm is greatly improved.

[Light and heat resistance]
The light resistance and heat resistance of the tetraphenylnaphthalocyanine compound of the present invention and the comparative compound were measured by the following measuring methods. The results are shown in Table 7.
(Light / heat resistance test measurement method)
To 95.0 g of toluene, 0.1 g of the tetraphenylnaphthalocyanine compound or comparative compound of the present invention produced in the above example and 5.0 g of methacrylic resin Delpet (registered trademark) manufactured by Asahi Kasei Chemicals Co., Ltd. are added. A dye resin solution was prepared by mixing and dissolving. Using a spin coater (manufactured by Kyoei Semiconductor Co., Ltd .: Spinner IH-III-A), this dye resin solution was applied onto a glass substrate so that the dye concentration was 20 wt% and the dry film thickness was 2 μm, and the temperature was 100 ° C. for 3 minutes. Dried.
The absorption spectrum of the coating glass plate thus obtained was measured with a spectrophotometer (manufactured by Hitachi, Ltd .: Spectrophotometer U-3500), and this was used as the spectrum before the test. Next, the coated glass plate whose spectrum was measured before the test was irradiated with 550 W / h of light for 200 hours using a xenon light resistance tester (manufactured by Toyo Seiki Co., Ltd .: Suntest XLS +). The absorption spectrum of the light-irradiated coated glass plate was measured with a spectrophotometer to obtain a spectrum after a light resistance test.

In the heat resistance test, the coated glass plate whose spectrum was measured before the test was heat-treated at a temperature of 100 ° C. for 200 hours with a thermostat (manufactured by Yamato Scientific Co., Ltd .: IG400). The absorption spectrum of the heat-treated coated glass plate was measured with a spectrophotometer to obtain a spectrum after the heat resistance test. In each spectrum before and after the heat resistance and light resistance test thus measured, the absorbance values in the range of 400 to 900 nm were integrated, and the difference between the values before and after the light resistance and heat resistance test was calculated.
The absorbance difference ΔE before and after the light resistance / heat resistance test was expressed by the following formula.
ΔΕ (%) = {Σ (400 to 900 nm of E1) −Σ (400 to 900 nm of E2)} / Σ (400 to 900 nm of E1) × 100
Note that E1: spectrum before test, E2: spectrum after test, and Σ: integration of absorbance values. The greater the value of ΔΕ, the greater the spectral change before and after the light and heat resistance test.
As shown in Table 7, all of the compounds of the examples exhibited excellent light resistance and heat resistance as compared with the comparative examples.
Further, from the comparison of the evaluation results of the isomers isolated in Examples 16 and 17, the isomers of the general formula (1) -a are represented by the general formulas (1) -b and (1) -c. Compared to isomers or a mixture of isomers, it showed particularly high light resistance and heat resistance.
In particular, Compound (1) -41-a, which is an isomer of the general formula (1) -a of the tetraphenylnaphthalocyanine compound whose central metal is copper, exhibited very high light resistance and heat resistance.

[Example 21] Production of heat ray shielding film 5 parts by weight of tetraphenylnaphthalocyanine compound (specific example (1) -7) produced in Example 9, acrylic resin LP-45M (product name, manufactured by Soken Chemical Co., Ltd.) 50 Part by weight, 20 parts by weight of methyl ethyl ketone, and 20 parts by weight of toluene were mixed and stirred to produce a resin composition.
The resin composition was coated on a polyethylene terephthalate film (PET film) having a thickness of 100 μm as a transparent substrate so as to have a thickness of 2.5 μm, and then dried at 100 ° C. for 3 minutes.
Furthermore, a transparent acrylic copolymer adhesive was applied to the other side of the PET film (the side not coated with the resin composition) with a bar thickness of 20 μm and dried and cured at 100 ° C. for 3 minutes. After that, a release film was stuck on the pressure-sensitive adhesive surface to produce a heat ray shielding film.
[Example 22] Production of heat ray shielding film Example 21 except that the compound of the specific example (1) -8 was used as the tetraphenylnaphthalocyanine compound instead of the compound of the specific example (1) -7. In the same manner as described above, a heat ray shielding film was produced.

[Example 23] Production of heat-shielding film In Example 21, Example 21 was used except that the compound of Example (1) -26 was used instead of the compound of Example (1) -7 as the tetraphenylnaphthalocyanine compound. In the same manner as described above, a heat ray shielding film was produced.
[Example 24] Production of heat ray shielding film In Example 21, Example 21 was used except that the compound of Example (1) -27 was used instead of the compound of Example (1) -7 as the tetraphenylnaphthalocyanine compound. In the same manner as described above, a heat ray shielding film was produced.

[Example 25] Production of heat ray shielding film In Example 21, Example 21 was used except that the compound of Specific Example (1) -35 was used instead of the compound of Specific Example (1) -7 as the tetraphenylnaphthalocyanine compound. In the same manner as described above, a heat ray shielding film was produced.
[Example 26] Production of heat ray shielding film In Example 21, Example 21 was used except that the compound of Specific Example (1) -37 was used instead of the compound of Specific Example (1) -7 as the tetraphenylnaphthalocyanine compound. In the same manner as described above, a heat ray shielding film was produced.
[Example 27] Production of heat ray shielding film In Example 21, Example 21 was used except that the compound of Specific Example (1) -41 was used instead of the compound of Specific Example (1) -7 as the tetraphenylnaphthalocyanine compound. In the same manner as described above, a heat ray shielding film was produced.

[Comparative Example 3] Production of heat ray shielding film In Example 21, the same operation as in Example 21 was conducted except that the compound of Comparative Example 1 was used instead of the compound of Specific Example (1) -7 as the tetraphenylnaphthalocyanine compound. A heat ray shielding film was manufactured.
[Comparative Example 4] Production of heat ray shielding film In Example 21, the same operation as in Example 21 was performed except that the compound of Comparative Example 2 was used instead of the compound of Specific Example (1) -7 as the tetraphenylnaphthalocyanine compound. A heat ray shielding film was manufactured.

The following items were evaluated for the heat ray shielding films produced in Examples 21 to 27 and Comparative Examples 3 and 4. The results are shown in Table 8 below.
In addition, in the evaluation test, the peeling film of the manufactured heat ray shielding film was peeled off and pressure-bonded to a glass plate having a thickness of 5 cm × 5 cm × 3 mm to prepare a test piece, which was used.
[Tts]
A U-3500 self-recording spectrophotometer manufactured by Hitachi, Ltd. is used as a measuring instrument, and laminated glass according to JIS R3106 “Testing method for transmittance, reflectance, emissivity, and solar heat gain of plate glass” The Tts of the sample was measured.
Tts (Total solar energy transmitted through a glazing) represents the total solar transmittance, and the smaller the value, the higher the heat shielding ability.

[Light and heat resistance]
In the light resistance test, the absorption spectrum of the test piece was measured with a spectrophotometer (manufactured by Hitachi, Ltd .: Spectrophotometer U-3500, which was used as the spectrum before the light resistance test. Next, the spectrum before the test was measured. The test piece was irradiated with light of 550 W / h for 200 hours using a xenon light resistance tester (manufactured by Toyo Seiki Co., Ltd .: Suntest XLS +), and the absorption spectrum of the light irradiated test piece was measured with a spectrophotometer. The spectrum was taken after the test.
In the heat resistance test, a test piece whose spectrum before the test was measured in the same manner as described above was heat-treated at a temperature of 100 ° C. for 200 hours with a thermostatic chamber (manufactured by Yamato Kagaku Co., Ltd .: IG400). The absorption spectrum of the heat-treated test piece was measured with a spectrophotometer to obtain a spectrum after the heat resistance test.
In each spectrum before and after the light / heat resistance test thus measured, the absorbance values in the range of 400 to 900 nm were integrated, and the difference between the values before and after the light / heat resistance test was calculated.
The absorbance difference ΔE before and after the light resistance / heat resistance test was expressed by the following formula.
ΔΕ (%) = {Σ (400 to 900 nm of E1) −Σ (400 to 900 nm of E2)} / Σ (400 to 900 nm of E1) × 100
Note that E1: spectrum before test, E2: spectrum after test, and Σ: integration of absorbance values.
The greater the value of ΔΕ, the greater the spectral change before and after the light and heat resistance test.
As shown in Table 8, all of the heat ray shielding films of the Examples exhibited superior characteristics in terms of heat shielding ability, light resistance and heat resistance as compared with Comparative Examples. In particular, it was very excellent in light resistance and heat resistance.

[Example 28] Preparation of interlayer film for laminated glass and laminated glass <Preparation of interlayer film for laminated glass>
As an organic ester plasticizer, 0.013 part by weight of the tetraphenylnaphthalocyanine compound (specific example (1) -7) produced in Example 9 was dissolved in 40 parts by weight of triethylene glycol-di-2-ethylhexanoate. This solution was added to 100 parts by weight of a polyvinyl butyral resin (trade name: BH-3, manufactured by Sekisui Chemical Co., Ltd.), sufficiently melt-kneaded with a mixing roll, and then extruded using an extruder to obtain a thickness of 0. An intermediate film of .76 mm was obtained.
<Production of laminated glass>
The above interlayer film is cut into a size of 100 mm × 100 mm, sandwiched between heat ray absorbing plate glasses (length 100 mm × width 100 mm × thickness 2.0 mm) according to JIS R3208, put in a rubber bag, and a vacuum degree of 2.6 kPa After degassing for 20 minutes, it was transferred to an oven while being degassed, and further vacuum-pressed by holding at 90 ° C. for 30 minutes. Then, it pressure-bonded for 20 minutes on the conditions of the temperature of 130 degreeC, and the pressure of 1.3 MPa in the autoclave, and the sample of the laminated glass was obtained.
[Example 29] Preparation of interlayer film for laminated glass and laminated glass In Example 28, the compound of the specific example (1) -8 was used as the tetraphenylnaphthalocyanine compound instead of the compound of the specific example (1) -7. Except for the above, the same operation as in Example 28 was performed to produce an interlayer film for laminated glass and a laminated glass.

[Example 30] Preparation of interlayer film for laminated glass and laminated glass In Example 28, the compound of the specific example (1) -34 was used in place of the compound of the specific example (1) -7 as the tetraphenylnaphthalocyanine compound. Except for the above, the same operation as in Example 28 was performed to produce an interlayer film for laminated glass and a laminated glass.
[Example 31] Preparation of interlayer film for laminated glass and laminated glass In Example 28, the compound of specific example (1) -36 was used as the tetraphenylnaphthalocyanine compound instead of the compound of specific example (1) -7. Except for the above, the same operation as in Example 28 was performed to produce an interlayer film for laminated glass and a laminated glass.
[Example 32] Preparation of interlayer film for laminated glass and laminated glass In Example 28, the compound of specific example (1) -26 was used in place of the compound of specific example (1) -7 as the tetraphenylnaphthalocyanine compound. Except for the above, the same operation as in Example 28 was performed to produce an interlayer film for laminated glass and a laminated glass.

[Example 33] Preparation of interlayer film for laminated glass and laminated glass In Example 28, the compound of specific example (1) -27 was used in place of the compound of specific example (1) -7 as the tetraphenylnaphthalocyanine compound. Except for the above, the same operation as in Example 28 was performed to produce an interlayer film for laminated glass and a laminated glass.
[Example 34] Preparation of interlayer film for laminated glass and laminated glass In Example 28, the compound of the specific example (1) -29 was used in place of the compound of the specific example (1) -7 as the tetraphenylnaphthalocyanine compound. Except for the above, the same operation as in Example 28 was performed to produce an interlayer film for laminated glass and a laminated glass.

[Example 35] Preparation of interlayer film for laminated glass and laminated glass In Example 28, the compound of specific example (1) -37 was used instead of the compound of specific example (1) -7 as the tetraphenylnaphthalocyanine compound. Except for the above, the same operation as in Example 28 was performed to produce an interlayer film for laminated glass and a laminated glass.
[Example 36] Preparation of interlayer film for laminated glass and laminated glass In Example 28, Compound (1) -37-a was used instead of the compound of Specific Example (1) -7 as the tetraphenylnaphthalocyanine compound. Were operated in the same manner as in Example 28 to produce an interlayer film for laminated glass and laminated glass.
[Example 37] Preparation of interlayer film for laminated glass and laminated glass In Example 28, compound (1) -37-b was used as the tetraphenylnaphthalocyanine compound instead of the compound of specific example (1) -7. Were operated in the same manner as in Example 28 to produce an interlayer film for laminated glass and laminated glass.

[Example 38] Preparation of interlayer film for laminated glass and laminated glass In Example 28, Compound (1) -37-c was used instead of the compound of Specific Example (1) -7 as the tetraphenylnaphthalocyanine compound. Were operated in the same manner as in Example 28 to produce an interlayer film for laminated glass and laminated glass.
[Example 39] Preparation of interlayer film for laminated glass and laminated glass In Example 28, the compound of specific example (1) -41 was used instead of the compound of specific example (1) -7 as the tetraphenylnaphthalocyanine compound. Except for the above, the same operation as in Example 28 was performed to produce an interlayer film for laminated glass and a laminated glass.

[Example 40] Preparation of interlayer film for laminated glass and laminated glass In Example 28, Compound (1) -41-a was used as the tetraphenylnaphthalocyanine compound instead of the compound of Specific Example (1) -7. Were operated in the same manner as in Example 28 to produce an interlayer film for laminated glass and laminated glass.
[Example 41] Preparation of interlayer film for laminated glass and laminated glass In Example 28, compound (1) -41-b was used as the tetraphenylnaphthalocyanine compound instead of the compound of specific example (1) -7. Were operated in the same manner as in Example 28 to produce an interlayer film for laminated glass and laminated glass.
[Example 42] Preparation of interlayer film for laminated glass and laminated glass In Example 28, compound (1) -41-c was used instead of the compound of specific example (1) -7 as the tetraphenylnaphthalocyanine compound. Were operated in the same manner as in Example 28 to produce an interlayer film for laminated glass and laminated glass.

[Example 43] Preparation of interlayer film for laminated glass and laminated glass In Example 28, the compound of specific example (1) -35 was used in place of the compound of specific example (1) -7 as the tetraphenylnaphthalocyanine compound. Except for the above, the same operation as in Example 28 was performed to produce an interlayer film for laminated glass and a laminated glass.
[Example 44] Preparation of interlayer film for laminated glass and laminated glass In Example 28, the compound of the specific example (1) -64 was used as the tetraphenylnaphthalocyanine compound instead of the compound of the specific example (1) -7. Except for the above, the same operation as in Example 28 was performed to produce an interlayer film for laminated glass and a laminated glass.

[Example 45] Preparation of interlayer film for laminated glass and laminated glass In Example 28, the compound of Specific Example (1) -65 was used as the tetraphenylnaphthalocyanine compound instead of the compound of Specific Example (1) -7. Except for the above, the same operation as in Example 28 was performed to produce an interlayer film for laminated glass and a laminated glass.
[Comparative Example 5] Preparation of interlayer film for laminated glass and laminated glass In Example 28, Example 28 was used except that the compound of Comparative Example 1 was used instead of the compound of Specific Example (1) -7 as the tetraphenylnaphthalocyanine compound. In the same manner as described above, an interlayer film for laminated glass and a laminated glass were produced.
[Comparative Example 6] Preparation of interlayer film for laminated glass and laminated glass In Example 28, Example 28 was used except that the compound of Comparative Example 2 was used in place of the compound of Specific Example (1) -7 as the tetraphenylnaphthalocyanine compound. In the same manner as described above, an interlayer film for laminated glass and a laminated glass were produced.

The following items were evaluated for the laminated glass samples prepared in Examples 28 to 45 and Comparative Examples 5 and 6. The results are shown in Table 9 below.
[Tts]
A U-3500 self-recording spectrophotometer manufactured by Hitachi, Ltd. is used as a measuring instrument, and laminated glass according to JIS R3106 “Testing method for transmittance, reflectance, emissivity, and solar heat gain of plate glass” The Tts of the sample was measured.
[Visible light transmittance]
Using a U-3500 self-recording spectrophotometer manufactured by Hitachi, Ltd. as a measuring instrument, the visible light transmittance at a wavelength of 380 to 780 nm of a laminated glass sample is measured according to JIS R 3212 “Safety glass test method for automobiles”. It was measured.

[Light and heat resistance]
In the light resistance test, the absorption spectrum of the laminated glass was measured with a spectrophotometer (manufactured by Hitachi, Ltd .: Spectrophotometer U-3500, which was used as the spectrum before the light resistance test. Next, the spectrum before the test was measured. The laminated glass was irradiated with light of 550 W / h for 200 hours using a xenon light resistance tester (manufactured by Toyo Seiki Co., Ltd .: Suntest XLS +). The spectrum after the light resistance test was taken.
In the heat resistance test, the laminated glass whose spectrum before the test was measured in the same manner as described above was heat-treated at a temperature of 100 ° C. for 200 hours with a thermostat (manufactured by Yamato Scientific Co., Ltd .: IG400). The absorption spectrum of the heat-treated laminated glass was measured with a spectrophotometer to obtain a spectrum after the heat resistance test.
In each spectrum before and after the light / heat resistance test thus measured, the absorbance values in the range of 400 to 900 nm were integrated, and the difference between the values before and after the light / heat resistance test was calculated.
The difference ΔE in absorbance before and after the light resistance / heat resistance test was expressed by the following equation.
ΔΕ (%) = {Σ (400 to 900 nm of E1) −Σ (400 to 900 nm of E2)} / Σ (400 to 900 nm of E1) × 100
Note that E1: spectrum before test, E2: spectrum after test, and Σ: integration of absorbance values. The greater the value of ΔΕ, the greater the spectral change before and after the light and heat resistance test.

As shown in Table 9, the laminated glasses of Examples 28 to 45 using the tetraphenylnaphthalocyanine compound of the present invention compared to Comparative Examples 5 and 6 are all heat-shielding ability, visible light transmittance, and light resistance. In addition, it showed excellent characteristics in heat resistance. In particular, it was very excellent in light resistance and heat resistance.
Moreover, as shown in Examples 35 to 42, the laminated glass using the isomer of the general formula (1) -a is an isomer of the general formula (1) -b or the general formula (1) -c, Or it showed especially high light resistance and heat resistance compared with the laminated glass using the mixture of each isomer.
In particular, a laminated glass using compound (1) -41-a, which is an isomer of general formula (1) -a of a tetraphenylnaphthalocyanine compound whose central metal is copper, has very high light resistance and heat resistance. showed that.

The tetraphenylnaphthalocyanine compound of the present invention has strong absorption in the near infrared region, very small absorption in the visible light region, good solubility in organic solvents and resins, light resistance, heat resistance, etc. Very high durability.
Therefore, it is used for applications such as near-infrared cut filters, transparent ink used for security, heat ray shielding films used for automobiles and building windows, interlayer films for laminated glass, infrared thermosensitive recording materials, plastic laser welding, etc. It is very useful as a near infrared absorbing dye.

Claims (12)

A tetraphenylnaphthalocyanine compound represented by the general formula (1).

[In the formula (1), M represents two hydrogen atoms, a divalent metal, or a trivalent or tetravalent metal derivative, and R _{1 to} R ₄ each independently represents a hydrogen atom, a halogen atom, or an alkyl group. A represents formula (B). ]

Wherein (B), X _1, X ₂ are each independently a hydrogen atom or a fluorine atom and table to an alkyl group substituted, never X ₁ and X ₂ are not hydrogen atoms at the same time, also, R ₁ ~ R ₄ is not a hydrogen atom at the same time . ] The tetraphenylnaphthalocyanine compound of Claim 1 which is at least 1 sort (s) chosen from general formula (1) -a- (1) -d.

[In the formulas (1) -a to (1) -d, M, R _{1 to} R ₄ and A have the same meanings as those in the general formula (1). ] The tetraphenyl naphthalocyanine compound of Claim 1 or 2 represented by General formula (1) -a.

[In the formula (1) -a, M, R _{1 to} R ₄ and A have the same meanings as those in the general formula (1). ] X _1, X ₂ is hydrogen atom or trifluoromethyl group, tetraphenyl naphthalocyanine compound according to any one of claims 1 to 3. The tetraphenyl naphthalocyanine compound according to any one of claims 1 to 4, wherein R _{1 to} R ₄ are a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms. 6. M according to any one of claims 1 to 5, wherein M is two hydrogen atoms, Pd, Cu, Zn, Pt, Ni, TiO, Co, Fe, Mn, Sn, Al-Cl, VO or In-Cl. Tetraphenylnaphthalocyanine compounds. It is represented by the general formula _{(1) -a, X 1,} X 2 are hydrogen atoms Komata is trifluoromethyl _group, a R 1 to R ₄ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, M The tetraphenylnaphthalocyanine compound according to claim 2 or 3, wherein is Cu. Represented by the general formula (1) -a, X ₁ and X ₂ are trifluoromethyl groups, R ₁ , R ₂ and R ₄ are hydrogen atoms, and R ₃ is a branched alkyl group having 3 to 8 carbon atoms. The tetraphenylnaphthalocyanine compound according to claim 2, 3 or 7, wherein M is Cu. A near-infrared absorbing material comprising the tetraphenylnaphthalocyanine compound according to claim 1. A heat ray shielding material comprising the tetraphenylnaphthalocyanine compound according to claim 1. The heat ray shielding material of Claim 10 which is a heat ray shielding film. The heat ray shielding material according to claim 10 , which is an interlayer film for laminated glass.

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